JP2019015954A - Antireflection film - Google Patents
Antireflection film Download PDFInfo
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- JP2019015954A JP2019015954A JP2018075365A JP2018075365A JP2019015954A JP 2019015954 A JP2019015954 A JP 2019015954A JP 2018075365 A JP2018075365 A JP 2018075365A JP 2018075365 A JP2018075365 A JP 2018075365A JP 2019015954 A JP2019015954 A JP 2019015954A
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- layer
- antireflection film
- low refractive
- inorganic nanoparticles
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- G02—OPTICS
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- G02B1/11—Anti-reflection coatings
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- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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Abstract
Description
関連出願との相互参照
本出願は、2016年3月9日付の韓国特許出願第10−2016−0028468号、2016年3月11日付の韓国特許出願第10−2016−0029336号、2016年3月14日付の韓国特許出願第10−2016−0030395号、および2017年3月9日付の韓国特許出願第10−2017−0029954号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示されたすべての内容は本明細書の一部として含まれる。
Cross-reference with related applications This application is filed with Korean Patent Application No. 10-2016-0028468 dated March 9, 2016, Korean Patent Application No. 10-2016-0029336 dated March 11, 2016, March 2016 Claims the benefit of priority based on Korean Patent Application No. 10-2016-0030395 dated 14 and Korean Patent Application No. 10-2017-0029954 dated March 9, 2017 and disclosed in the Korean patent application literature All the contents of this document are included as part of this specification.
本発明は、反射防止フィルムに関し、より詳しくは、低い反射率および高い透光率を有しかつ、高い耐スクラッチ性および防汚性を同時に実現することができ、ディスプレイ装置の画面の鮮明度を高めることができる反射防止フィルムに関する。 The present invention relates to an antireflection film. More specifically, the present invention has a low reflectance and a high translucency, and can simultaneously realize high scratch resistance and antifouling properties, thereby improving the screen clarity of a display device. The present invention relates to an antireflection film that can be enhanced.
一般に、PDP、LCDなどの平板ディスプレイ装置には、外部から入射する光の反射を最小化するための反射防止フィルムが装着される。 In general, a flat display device such as a PDP or LCD is provided with an antireflection film for minimizing reflection of light incident from the outside.
光の反射を最小化するための方法としては、樹脂に無機微粒子などのフィラーを分散させて基材フィルム上にコーティングし、凹凸を付与する方法(anti−glare:AGコーティング);基材フィルム上に屈折率が異なる多数の層を形成させて光の干渉を利用する方法(anti−reflection:ARコーティング)、またはこれらを混用する方法などがある。 As a method for minimizing the reflection of light, a method in which fillers such as inorganic fine particles are dispersed in a resin and coated on a base film to give unevenness (anti-glare: AG coating); on the base film There are a method in which a number of layers having different refractive indexes are formed and light interference is utilized (anti-reflection: AR coating), or a method in which these are mixed.
そのうち、前記AGコーティングの場合、反射する光の絶対量は、一般的なハードコートと同等の水準であるが、凹凸を通した光の散乱を利用して目に入る光の量を低減することによって低反射効果を得ることができる。しかし、前記AGコーティングは表面凹凸によって画面の鮮明度が落ちるため、最近はARコーティングに対する多くの研究がなされている。 Among them, in the case of the AG coating, the absolute amount of the reflected light is the same level as that of a general hard coat, but the amount of light entering the eye is reduced by using the scattering of light through the unevenness. Thus, a low reflection effect can be obtained. However, since the AG coating deteriorates the sharpness of the screen due to surface irregularities, many studies on the AR coating have been made recently.
前記ARコーティングを利用したフィルムとしては、基材フィルム上にハードコート層(高屈折率層)、低反射コーティング層などが積層された多層構造のものが商用化されている。しかし、前記のように多数の層を形成させる方法は、各層を形成する工程を別途に行うことによって、層間密着力(界面接着力)が弱く耐スクラッチ性が低下するという欠点がある。 As a film using the AR coating, a film having a multilayer structure in which a hard coat layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a base film is commercially available. However, the method of forming a large number of layers as described above has a drawback in that by separately performing the process of forming each layer, the interlayer adhesion (interface adhesion) is weak and the scratch resistance is reduced.
また、従来は、反射防止フィルムに含まれる低屈折層の耐スクラッチ性を向上させるためには、ナノメートルサイズの多様な粒子(例えば、シリカ、アルミナ、ゼオライトなどの粒子)を添加する方法が主に試みられた。しかし、前記のようなナノメートルサイズの粒子を用いる場合、低屈折層の反射率を低下させながら耐スクラッチ性を同時に高めにくい限界があり、ナノメートルサイズの粒子によって低屈折層表面が有する防汚性が大きく低下した。 In addition, conventionally, in order to improve the scratch resistance of the low refractive layer contained in the antireflection film, a method of adding various nanometer-sized particles (for example, particles of silica, alumina, zeolite, etc.) has been mainly used. Attempted to. However, when nanometer-sized particles as described above are used, there is a limit that it is difficult to simultaneously improve the scratch resistance while lowering the reflectance of the low-refractive layer. The characteristics were greatly reduced.
これにより、外部から入射する光の絶対反射量を低減し、表面の耐スクラッチ性と共に防汚性を向上させるための多くの研究がなされているが、それによる物性改善の程度が不十分である。 As a result, many studies have been made to reduce the amount of absolute reflection of light incident from the outside and improve the antifouling property as well as the scratch resistance of the surface, but the degree of improvement in physical properties is insufficient. .
本発明は、低い反射率および高い透光率を有しかつ、高い耐スクラッチ性および防汚性を同時に実現することができ、ディスプレイ装置の画面の鮮明度を高めることができる反射防止フィルムを提供する。 The present invention provides an antireflection film that has a low reflectance and a high light transmittance, can simultaneously realize high scratch resistance and antifouling properties, and can enhance the clarity of the screen of a display device. To do.
本明細書では、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、表面から35nm〜55nmの厚さ(thickness)で1つの極値を示し、表面から85nm〜105nmの厚さ(thickness)で1つの極値を示す、反射防止フィルムが提供される。 In this specification, in the Fourier transform analysis (Fourier transform analysis) result graph with respect to the measurement result of the X-ray reflectivity by Cu-Kα ray, one extreme value is shown with a thickness (thickness) of 35 nm to 55 nm from the surface. An antireflective film is provided that exhibits one extreme at a thickness of from 85 nm to 105 nm.
以下、発明の具体的な実現例による反射防止フィルムに関してより詳細に説明する。 Hereinafter, the antireflection film according to a specific implementation example of the invention will be described in more detail.
本明細書において、光重合性化合物は、光が照射されると、例えば、可視光線または紫外線が照射されると、重合反応を起こす化合物を通称する。 In the present specification, a photopolymerizable compound is a compound that causes a polymerization reaction when irradiated with light, for example, when irradiated with visible light or ultraviolet light.
また、含フッ素化合物は、化合物のうちの少なくとも1個以上のフッ素元素が含まれている化合物を意味する。 The fluorine-containing compound means a compound containing at least one fluorine element among the compounds.
また、(メタ)アクリル[(Meth)acryl]は、アクリル(acryl)およびメタクリル(Methacryl)の両方ともを含む意味である。 Further, (meth) acryl [(Meth) acryl] includes both acrylic and methacryl.
また、(共)重合体は、共重合体(co−polymer)および単独重合体(homo−polymer)の両方ともを含む意味である。 Further, the (co) polymer is meant to include both a copolymer (co-polymer) and a homopolymer (homo-polymer).
さらに、中空シリカ粒子(silica hollow particles)とは、ケイ素化合物または有機ケイ素化合物から導出されるシリカ粒子であって、前記シリカ粒子の表面および/または内部に空き空間が存在する形態の粒子を意味する。 Further, the hollow silica particles means silica particles derived from a silicon compound or an organosilicon compound and having a form in which a free space exists on the surface and / or inside of the silica particles. .
発明の一実現例によれば、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、表面から35nm〜55nmの厚さ(thickness)で1つの極値を示し、表面から85nm〜105nmの厚さ(thickness)で1つの極値を示す、反射防止フィルムが提供される。 According to an embodiment of the invention, in the Fourier transform analysis result graph for the measurement result of the X-ray reflectivity by Cu-Kα ray, one extreme value at a thickness (thickness) of 35 nm to 55 nm from the surface. An antireflection film is provided that exhibits one extreme value at a thickness of 85 nm to 105 nm from the surface.
そこで、本発明者らは、反射防止フィルムに関する研究を進行させて、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、表面から35nm〜55nmの厚さ(thickness)で1つの極値を示し、表面から85nm〜105nmの厚さ(thickness)で1つの極値を示す反射防止フィルムは、低い反射率および高い透光率を有しかつ、高い耐スクラッチ性および防汚性を同時に実現できるという点を、実験を通して確認して、発明を完成した。 Therefore, the present inventors proceeded with research on the antireflection film, and in the Fourier transform analysis (Fourier transform analysis) result graph with respect to the measurement result of the X-ray reflectivity by Cu-Kα ray, the thickness from the surface to 35 nm to 55 nm. An antireflection film that exhibits one extreme value in thickness and one extreme value in the thickness of 85 nm to 105 nm from the surface has low reflectance and high transmissivity, and has high resistance. It was confirmed through experiments that the scratch and antifouling properties could be realized simultaneously, and the invention was completed.
具体的には、前記反射防止フィルムに対するCu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフは、X軸のフィルムの厚さ(thickness)に対するY軸のフーリエ変換強度(Fourier transform magnitude)を示す。 Specifically, the Fourier transform analysis result graph for the measurement result of the X-ray reflectivity by Cu-Kα rays for the antireflection film is a Fourier transform of the Y axis with respect to the thickness of the X axis film. The transform strength (Fourier transform magnitude) is shown.
前記フーリエ変換強度の極値は、厚さ方向への電子密度の変化に関係し、上述した表面から35nm〜55nmの厚さ(thickness)で1つのフーリエ変換強度の極値を示し、表面から85nm〜105nmの厚さ(thickness)で1つのフーリエ変換強度の極値を示すと、フィルムの厚さ方向に電子密度が異なる2つの層が存在しかつ、より低い反射率を実現することができ、耐スクラッチ特性および防汚性の向上も共に実現可能である。 The extreme value of the Fourier transform intensity is related to the change of the electron density in the thickness direction, and shows one extreme value of the Fourier transform intensity at a thickness of 35 nm to 55 nm from the surface described above, and 85 nm from the surface. When the extreme value of one Fourier transform intensity is shown at a thickness (thickness) of ˜105 nm, there are two layers having different electron densities in the thickness direction of the film, and a lower reflectance can be realized, Both improved scratch resistance and antifouling properties can be achieved.
具体的には、前記反射防止フィルムは、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、表面から35nm〜55nmの厚さ(thickness)で1つの極値を示し、表面から85nm〜105nmの厚さ(thickness)で1つの極値を示すことによって、内部に最適化された電子密度および屈折率分布を維持することができ、これによって、より低い反射率を実現し、スクラッチまたは外部汚染物質に対して相対的に安定した構造を有することができる。 Specifically, the antireflection film has a thickness (thickness) of 35 nm to 55 nm from the surface in a Fourier transform analysis result graph for the measurement result of the X-ray reflectivity by Cu-Kα ray. By showing an extreme value and showing one extreme value with a thickness of 85 nm to 105 nm from the surface, an internally optimized electron density and refractive index profile can be maintained, thereby lowering It can achieve reflectivity and have a structure that is relatively stable against scratches or external contaminants.
前記極値は、前記反射防止フィルムに対するCu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、y軸に相当する反射率のフーリエ変換解析強度方向に膨らんで現れる地点(point)を意味する。 The extreme value swells in the Fourier transform analysis intensity graph of the reflectance corresponding to the y-axis in the Fourier transform analysis result graph for the measurement result of the X-ray reflectivity by Cu-Kα rays for the antireflection film. It means a point that appears at.
より具体的には、前記極値(extremal value)は、前記反射防止フィルムに対するCu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフに現れる「X軸の厚さ(thickness)に対するY軸のフーリエ変換強度(Fourier transform magnitude)」の関数値が、周辺関数値と比較した時、最も大きいか小さい場合であり、例えば、「X軸の厚さ(thickness)に対するY軸のフーリエ変換強度(Fourier transform magnitude)」の関数を微分した値が0の地点を意味する。また、前記極値(extremal value)は、極大値(Local Maximum)を意味することができる。 More specifically, the extreme value is expressed by a “X-axis thickness” which appears in a Fourier transform analysis result graph for an X-ray reflectivity measurement result by Cu—Kα rays for the antireflection film. This is a case where the function value of the Fourier transform strength of the Y-axis with respect to the thickness (thickness) is the largest or the smallest when compared with the peripheral function value, for example, with respect to the thickness of the X-axis (thickness) It means a point where the value obtained by differentiating the function of “Fourier transform magnitude” on the Y axis is zero. In addition, the extreme value may mean a local maximum.
前記Cu−Kα線によるX線反射率の測定は、1cm×1cm(横×縦)の大きさの反射防止フィルムに対して、1.5418Åの波長のCu−Kα線を用いて測定することができる。具体的には、2theta(2θ)値が0となるようにサンプルステージを調整した後、サンプルのhalf−cutを確認し、この後、入射角と反射角がspecular条件を満足する状態で反射率測定を行って、X線反射率パターンを測定する。 The measurement of the X-ray reflectivity using the Cu-Kα ray can be performed using an Cu-Kα ray having a wavelength of 1.5418 mm with respect to an antireflection film having a size of 1 cm × 1 cm (width × length). it can. Specifically, after adjusting the sample stage so that the 2theta (2θ) value becomes 0, the half-cut of the sample is confirmed, and then the reflectance is measured in a state where the incident angle and the reflection angle satisfy the spectral condition. Measurement is performed to measure the X-ray reflectivity pattern.
前記Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析は、PANalytical社のX’pert Reflectivityプログラムを用いて行うことができる。具体的には、フーリエ変換時、input値としては、start angle、end angle、critical angleがあり、例えば、start angleには0.1°を入力し、end angleには1.2°を入力し、critical angleには0.163°または0.18°を入力することができる。 The Fourier transform analysis for the measurement result of the X-ray reflectivity by the Cu-Kα ray can be performed by using X'pert Reflectivity program of PANalytical. Specifically, at the time of Fourier transform, there are start angle, end angle, and critical angle as input values. For example, 0.1 ° is input to start angle, and 1.2 ° is input to end angle. , Critical angle can be 0.163 ° or 0.18 °.
一方、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、35nm〜55nmの厚さ(thickness)で1つの極値を示し、85nm〜105nmの厚さ(thickness)で1つの極値を示す前記反射防止フィルムの特性は、反射防止フィルムに含まれる成分、光学特性、表面特性および内部特性などを調節して達成することができる。 On the other hand, in the Fourier transform analysis result graph for the measurement result of the X-ray reflectivity by Cu-Kα ray, one extreme value is shown with a thickness of 35 nm to 55 nm, and a thickness of 85 nm to 105 nm. The properties of the antireflection film exhibiting one extreme value in (thickness) can be achieved by adjusting the components, optical properties, surface properties, internal properties and the like contained in the antireflection film.
前記実現例の反射防止フィルムは、通常知られた細部構成を含むことができ、例えば、前記反射防止フィルムは、ハードコート層;および前記ハードコート層上に形成された低屈折層;を含むことができ、必要に応じて、他の特性を有する層を1つ以上さらに含んでもよい。 The antireflection film of the implementation may include a generally known detail structure, for example, the antireflection film includes a hard coat layer; and a low refractive layer formed on the hard coat layer. And may further include one or more layers having other properties as required.
前記表面から35nm〜55nmの厚さおよび85nm〜105nmそれぞれは、前記反射防止フィルムの表面から定義または測定される厚さであり、上述のように、前記反射防止フィルムは、ハードコート層;および前記ハードコート層上に形成された低屈折層を含む場合、前記表面から35nm〜55nmの厚さおよび85nm〜105nmそれぞれは、前記低屈折層の表面からの厚さであってもよい。 35 nm to 55 nm from the surface and 85 nm to 105 nm respectively are thicknesses defined or measured from the surface of the antireflection film, and as described above, the antireflection film comprises a hard coat layer; and When the low refractive layer formed on the hard coat layer is included, the thickness of 35 nm to 55 nm and the thickness of 85 nm to 105 nm from the surface may be the thickness from the surface of the low refractive layer, respectively.
より具体的には、前記反射防止フィルムは、ハードコート層;およびバインダー樹脂と前記バインダー樹脂に分散した中空状無機ナノ粒子およびソリッド状無機ナノ粒子を含む低屈折層;を含むことができる。 More specifically, the antireflection film may include a hard coat layer; and a low refractive layer including a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.
具体的には、前記反射防止フィルムにおいて、前記ハードコート層および前記低屈折層の間の界面近くにソリッド状無機ナノ粒子が中空状無機ナノ粒子より多く分布し得る。 Specifically, in the antireflection film, more solid inorganic nanoparticles can be distributed near the interface between the hard coat layer and the low refractive layer than hollow inorganic nanoparticles.
従来は、反射防止フィルムの耐スクラッチ性を高めるために無機粒子を過剰添加したが、反射防止フィルムの耐スクラッチ性を高めるのに限界があり、むしろ反射率と防汚性が低下する問題点があった。 Conventionally, inorganic particles are excessively added to improve the scratch resistance of the antireflection film, but there is a limit to improving the scratch resistance of the antireflection film, and there is a problem that the reflectance and antifouling properties are rather lowered. there were.
これに対し、前記反射防止フィルムに含まれる低屈折層内で中空状無機ナノ粒子およびソリッド状無機ナノ粒子が互いに区分可能に分布させる場合、低い反射率および高い透光率を有しかつ、高い耐スクラッチ性および防汚性を同時に実現することができる。 On the other hand, when the hollow inorganic nanoparticles and the solid inorganic nanoparticles are distributed so as to be separable from each other in the low refractive layer included in the antireflection film, they have a low reflectance and a high light transmittance and are high. Scratch resistance and antifouling properties can be realized at the same time.
具体的には、前記反射防止フィルムの低屈折層のうち、前記ハードコート層および前記低屈折層の間の界面近くにソリッド状無機ナノ粒子を主に分布させ、前記界面の反対面側には中空状無機ナノ粒子を主に分布させる場合、従来無機粒子を用いて得られていた実際の反射率に比べてより低い反射率を達成することができ、また、前記低屈折層が大きく向上した耐スクラッチ性および防汚性を共に実現することができる。 Specifically, among the low refractive layers of the antireflection film, solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low refractive layer, and on the opposite surface side of the interface. When the hollow inorganic nanoparticles are mainly distributed, it is possible to achieve a lower reflectivity than the actual reflectivity obtained by using conventional inorganic particles, and the low refractive layer is greatly improved. Both scratch resistance and antifouling properties can be realized.
また、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、35nm〜55nmの厚さ(thickness)で1つの極値を示し、85nm〜105nmの厚さ(thickness)で1つの極値を示す前記反射防止フィルムの特性は、前記低屈折層の表面または内部特性によるものであり得る。 In addition, in the Fourier transform analysis result graph for the measurement result of the X-ray reflectivity by Cu-Kα ray, one extreme value is shown at a thickness of 35 nm to 55 nm, and a thickness of 85 nm to 105 nm. The characteristic of the antireflection film showing one extreme value in (thickness) may be due to the surface or internal characteristics of the low refractive layer.
上述のように、前記反射防止フィルムは、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、35nm〜55nmの厚さ(thickness)で1つの極値を示し、85nm〜105nmの厚さ(thickness)で1つの極値を示すことによって、内部に最適化された電子密度および屈折率分布を維持することができ、これによって、より低い反射率を実現し、スクラッチまたは外部汚染物質に対して相対的に安定した構造を有することができる。 As described above, the antireflection film has one extreme value at a thickness of 35 nm to 55 nm in a Fourier transform analysis result graph with respect to a measurement result of X-ray reflectance by Cu-Kα ray. By showing one extreme value with a thickness of 85 nm to 105 nm, it is possible to maintain an internally optimized electron density and refractive index distribution, thereby realizing lower reflectivity In addition, the structure can be relatively stable against scratches or external contaminants.
上述のように、前記低屈折層は、バインダー樹脂と前記バインダー樹脂に分散した中空状無機ナノ粒子およびソリッド状無機ナノ粒子を含み、前記ハードコート層の一面に形成されるが、前記ソリッド状無機ナノ粒子全体中の70体積%以上は、前記ハードコート層および前記低屈折層の間の界面から前記低屈折層全体厚さの50%以内に存在し得る。 As described above, the low refractive layer includes a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, and is formed on one surface of the hard coat layer. 70% by volume or more in the whole nanoparticles may be present within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.
「前記ソリッド状無機ナノ粒子全体中の70体積%以上が特定領域に存在する」とは、前記低屈折層の断面において、前記ソリッド状無機ナノ粒子が前記特定領域に大部分存在するとの意味で定義され、具体的には、前記ソリッド状無機ナノ粒子全体中の70体積%以上は、前記ソリッド状無機ナノ粒子全体の体積を測定して確認可能である。 “70% by volume or more of the whole solid inorganic nanoparticles are present in the specific region” means that the solid inorganic nanoparticles are mostly present in the specific region in the cross section of the low refractive layer. Specifically, 70% by volume or more in the whole solid inorganic nanoparticles can be confirmed by measuring the volume of the whole solid inorganic nanoparticles.
前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子が特定の領域に存在するか否かは、それぞれの中空状無機ナノ粒子またはソリッド状無機ナノ粒子が前記特定の領域内に粒子として存在するか否かで決定し、前記特定領域の境界面にわたって存在する粒子は除いて決定する。 Whether the hollow inorganic nanoparticle and the solid inorganic nanoparticle are present in a specific region is determined based on whether each hollow inorganic nanoparticle or solid inorganic nanoparticle is present as a particle in the specific region. It is determined by excluding particles existing over the boundary surface of the specific region.
また、上述のように、前記低屈折層において、前記ハードコート層および前記低屈折層の間の界面の反対面側には中空状無機ナノ粒子が主に分布し得るが、具体的には、前記中空状無機ナノ粒子全体中の30体積%以上、50体積%以上、または70体積%以上が、前記ソリッド状無機ナノ粒子全体より、前記ハードコート層および前記低屈折層の間の界面から前記低屈折層の厚さ方向により遠い距離に存在し得る。 Further, as described above, in the low refractive layer, hollow inorganic nanoparticles can be mainly distributed on the opposite surface side of the interface between the hard coat layer and the low refractive layer, specifically, 30% by volume or more, 50% by volume or more, or 70% by volume or more of the whole hollow inorganic nanoparticle is more than the whole solid inorganic nanoparticle from the interface between the hard coat layer and the low refractive layer. It may exist at a greater distance in the thickness direction of the low refractive layer.
より具体的には、前記ハードコート層と前記低屈折層との界面から前記低屈折層全体厚さの30%以内に前記ソリッド状無機ナノ粒子全体中の70体積%以上が存在し得る。また、前記ハードコート層と前記低屈折層との界面から前記低屈折層全体厚さの30%超過の領域に前記中空状無機ナノ粒子全体中の70体積%以上が存在し得る。 More specifically, 70% by volume or more of the entire solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. Further, 70% by volume or more of the whole hollow inorganic nanoparticles may be present in a region exceeding 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.
前記反射防止フィルムの低屈折層のうち、前記ハードコート層および前記低屈折層の間の界面近くにソリッド状無機ナノ粒子を主に分布させ、前記界面の反対面側には中空状無機ナノ粒子を主に分布させることによって、前記低屈折層内に互いに屈折率が異なる2つ以上の部分または2つ以上の層が形成され、これにより、前記反射防止フィルムの反射率が低くなり得る。 Of the low-refractive layer of the antireflection film, solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low-refractive layer, and hollow inorganic nanoparticles are provided on the opposite side of the interface. In the low-refractive layer, two or more portions or two or more layers having different refractive indexes are formed in the low-refractive layer, whereby the reflectance of the antireflection film can be lowered.
前記低屈折層において、前記ソリッド状無機ナノ粒子および中空状無機ナノ粒子の特異的分布は、後述の特定の製造方法において、前記ソリッド状無機ナノ粒子および中空状無機ナノ粒子の間の密度の差を調節し、前記2種のナノ粒子を含む低屈折層形成用光硬化性樹脂組成物を乾燥温度を調節することにより得られる。 In the low refractive layer, the specific distribution of the solid inorganic nanoparticles and the hollow inorganic nanoparticles is a difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles in a specific manufacturing method described later. The photocurable resin composition for forming a low refractive layer containing the two types of nanoparticles is adjusted to adjust the drying temperature.
具体的には、前記ソリッド状無機ナノ粒子が、前記中空状無機ナノ粒子に比べて0.50g/cm3以上高い密度を有することができ、また、前記ソリッド状無機ナノ粒子および前記中空状無機ナノ粒子の間の密度の差は、0.50g/cm3〜1.50g/cm3、または0.60g/cm3〜1.00g/cm3であってもよい。このような密度の差によって、前記ハードコート層上に形成される低屈折層において、前記ソリッド状無機ナノ粒子がハードコート層側により近い側に位置し得る。ただし、後述の製造方法や実施例などから確認されるように、前記2種の粒子間の密度の差にもかかわらず、所定の乾燥温度および時間を作用してこそ、上述した低屈折層内における粒子の分布様相を実現することができる。 Specifically, the solid inorganic nanoparticles can have a density higher by 0.50 g / cm 3 or more than the hollow inorganic nanoparticles, and the solid inorganic nanoparticles and the hollow inorganic nanoparticles can be used. the difference in density between the nanoparticles may be 0.50g / cm 3 ~1.50g / cm 3 or 0.60g / cm 3 ~1.00g / cm 3 ,. Due to such a density difference, in the low refractive layer formed on the hard coat layer, the solid inorganic nanoparticles can be located closer to the hard coat layer side. However, as confirmed from the manufacturing method and examples to be described later, in spite of the difference in density between the two kinds of particles, the above-described low refractive layer is not affected by the action of a predetermined drying temperature and time. It is possible to realize the distribution aspect of the particles.
前記反射防止フィルムの低屈折層のうち、前記ハードコート層および前記低屈折層の間の界面近くにソリッド状無機ナノ粒子を主に分布させ、前記界面の反対面側には中空状無機ナノ粒子を主に分布させる場合、従来無機粒子を用いて得られていた反射率より低い反射率を実現することができる。具体的には、前記反射防止フィルムは、380nm〜780nmの可視光線波長帯領域で1.5%以下、または1.0%以下、または0.50〜1.0%、0.7%以下、または0.60%〜0.70%、または0.62%〜0.67%の平均反射率を示すことができる。 Of the low-refractive layer of the antireflection film, solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low-refractive layer, and hollow inorganic nanoparticles are provided on the opposite side of the interface. In the case of distributing mainly, it is possible to realize a reflectance lower than that conventionally obtained by using inorganic particles. Specifically, the antireflection film is 1.5% or less, or 1.0% or less, or 0.50 to 1.0%, 0.7% or less in the visible light wavelength band region of 380 nm to 780 nm, Alternatively, an average reflectance of 0.60% to 0.70%, or 0.62% to 0.67% can be shown.
一方、前記実現例の反射防止フィルムにおいて、前記低屈折層は、前記ソリッド状無機ナノ粒子全体中の70体積%以上が含まれている第1層と、前記中空状無機ナノ粒子全体中の70体積%以上が含まれている第2層とを含むことができ、前記第1層が、第2層に比べて、前記ハードコート層および前記低屈折層の間の界面により近く位置し得る。 On the other hand, in the antireflection film of the implementation example, the low-refractive layer includes a first layer containing 70% by volume or more of the whole solid inorganic nanoparticles, and 70 of the whole hollow inorganic nanoparticles. A second layer containing at least vol%, and the first layer may be located closer to the interface between the hard coat layer and the low refractive layer than the second layer.
上述のように、前記反射防止フィルムの低屈折層では、前記ハードコート層および前記低屈折層の間の界面近くにソリッド状無機ナノ粒子が主に分布し、前記界面の反対面側には中空状無機ナノ粒子が主に分布するが、前記ソリッド状無機ナノ粒子および中空状無機ナノ粒子それぞれの主に分布する領域が低屈折層内で可視的に確認される独立した層を形成することができる。 As described above, in the low-refractive layer of the antireflection film, solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low-refractive layer, and hollow on the opposite surface side of the interface. Although the inorganic inorganic particles are mainly distributed, the solid inorganic nanoparticles and the hollow inorganic nanoparticles may form independent layers in which the main distribution regions are visually confirmed in the low refractive layer. it can.
また、前記ソリッド状無機ナノ粒子全体中の70体積%以上が含まれている第1層は、前記ハードコート層および前記低屈折層の間の界面から前記低屈折層全体厚さの50%以内に位置し得る。より具体的には、前記ハードコート層と前記低屈折層との界面から前記低屈折層全体厚さの30%以内に前記ソリッド状無機ナノ粒子全体中の70体積%以上が含まれている第1層が存在し得る。 The first layer containing 70% by volume or more of the whole solid inorganic nanoparticles is within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. Can be located. More specifically, 70% by volume or more of the entire solid inorganic nanoparticles is contained within 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. There can be one layer.
さらに、上述のように、前記低屈折層において、前記ハードコート層および前記低屈折層の間の界面の反対面側には中空状無機ナノ粒子が主に分布し得るが、具体的には、前記中空状無機ナノ粒子全体中の30体積%以上、または50体積%以上、または70体積%以上が、前記ソリッド状無機ナノ粒子全体より、前記ハードコート層および前記低屈折層の間の界面から前記低屈折層の厚さ方向により遠い距離に存在し得る。これにより、上述のように、前記第1層が、第2層に比べて、前記ハードコート層および前記低屈折層の間の界面により近く位置し得る。 Furthermore, as described above, in the low refractive layer, hollow inorganic nanoparticles can be mainly distributed on the opposite side of the interface between the hard coat layer and the low refractive layer, specifically, 30% by volume or more, 50% by volume or more, or 70% by volume or more of the whole hollow inorganic nanoparticle is from the interface between the hard coat layer and the low refractive layer from the whole solid inorganic nanoparticle. The low refractive layer may exist at a farther distance in the thickness direction. Accordingly, as described above, the first layer can be located closer to the interface between the hard coat layer and the low refractive layer than the second layer.
また、上述のように、前記ソリッド状無機ナノ粒子および中空状無機ナノ粒子それぞれが主に分布する領域である第1層および第2層それぞれが低屈折層内に存在する点を可視的に確認可能である。例えば、透過電子顕微鏡[Transmission Electron Microscope]または走査電子顕微鏡[Scanning Electron Microscope]などを用いて第1層および第2層それぞれが低屈折層内に存在する点を可視的に確認することができ、また、低屈折層内で第1層および第2層それぞれに分布するソリッド状無機ナノ粒子および中空状無機ナノ粒子の比率も確認可能である。 Further, as described above, it is visually confirmed that the first layer and the second layer, which are regions in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed, exist in the low refractive layer, respectively. Is possible. For example, the point where the first layer and the second layer are present in the low refractive layer can be visually confirmed using a transmission electron microscope (Scanning Electron Microscope) or a scanning electron microscope (Scanning Electron Microscope). Further, the ratio of the solid inorganic nanoparticles and the hollow inorganic nanoparticles distributed in the first layer and the second layer in the low refractive layer can also be confirmed.
一方、前記ソリッド状無機ナノ粒子全体中の70体積%以上が含まれている第1層、および前記中空状無機ナノ粒子全体中の70体積%以上が含まれている第2層それぞれは、1つの層内で共通した光学特性を共有することができ、これにより、1つの層と定義される。 Meanwhile, each of the first layer containing 70% by volume or more of the whole solid inorganic nanoparticles and the second layer containing 70% by volume or more of the whole hollow inorganic nanoparticles is 1 Common optical properties can be shared within two layers, thereby defining one layer.
より具体的には、前記第1層および第2層それぞれは、楕円偏光法(ellipsometry)で測定した偏極の楕円率を前記一般式1のコーシーモデル(Cauchy model)で最適化(fitting)した時、特定のコーシーパラメータA、BおよびCを有し、これにより、第1層および第2層は互いに区分可能である。また、前記楕円偏光法(ellipsometry)で測定した偏極の楕円率を下記一般式1のコーシーモデル(Cauchy model)で最適化(fitting)により前記第1層および第2層の厚さも導出できるため、前記低屈折層内における第1層および第2層の定義が可能になる。 More specifically, in each of the first layer and the second layer, the ellipticity of polarization measured by elliptic polarization was optimized using the Cauchy model of the general formula 1. Sometimes it has certain Cauchy parameters A, B and C, so that the first layer and the second layer are distinguishable from each other. In addition, the thicknesses of the first layer and the second layer can also be derived by optimizing the ellipticity of the polarization measured by the ellipsometry with the Cauchy model of the following general formula 1. The first layer and the second layer in the low refractive index layer can be defined.
前記一般式1において、n(λ)は、λ波長における屈折率(refractive index)であり、λは、300nm〜1800nmの範囲であり、A、BおよびCは、コーシーパラメータである。 In the general formula 1, n (λ) is a refractive index at λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B, and C are Cauchy parameters.
一方、前記楕円偏光法(ellipsometry)で測定した偏極の楕円率を前記一般式1のコーシーモデル(Cauchy model)で最適化(fitting)した時に導出されるコーシーパラメータA、BおよびCは、1つの層内における平均値であってもよい。これにより、前記第1層および第2層の間に界面が存在する場合、前記第1層および第2層が有するコーシーパラメータA、BおよびCの重なる領域が存在し得る。ただし、この場合にも、前記第1層および第2層それぞれが有するコーシーパラメータA、BおよびCの平均値を満足する領域に応じて、前記第1層および第2層の厚さおよび位置が特定される。 On the other hand, the Cauchy parameters A, B, and C derived when the ellipticity of the polarization measured by the ellipsometry is optimized by the Cauchy model of the general formula 1 are: It may be an average value within one layer. Thereby, when an interface exists between the first layer and the second layer, there may be a region where the Cauchy parameters A, B, and C included in the first layer and the second layer overlap. However, also in this case, the thickness and position of the first layer and the second layer depend on the area satisfying the average value of the Cauchy parameters A, B, and C of the first layer and the second layer, respectively. Identified.
例えば、前記低屈折層に含まれている第1層に対して、楕円偏光法(ellipsometry)で測定した偏極の楕円率を下記一般式1のコーシーモデル(Cauchy model)で最適化(fitting)した時、下記Aは1.0〜1.65、Bは0.0010〜0.0350、Cは0〜1×10−3の条件を満足することができ、また、前記低屈折層に含まれている第1層に対して、前記Aは1.30〜1.55、または1.40〜1.52、または1.491〜1.511、かつ、前記Bは0〜0.005、または0〜0.00580、または0〜0.00573、かつ、前記Cは0〜1×10−3、または0〜5.0×10−4、または0〜4.1352×10−4の条件を満足することができる。 For example, for the first layer included in the low refractive layer, the ellipticity of polarization measured by elliptic polarization is optimized by a Cauchy model of the following general formula 1 When A is 1.0 to 1.65, B is 0.0010 to 0.0350, C is 0 to 1 × 10 −3 , and is included in the low refractive layer. A is 1.30 to 1.55, or 1.40 to 1.52, or 1.491 to 1.511, and B is 0 to 0.005 with respect to the first layer. Or 0 to 0.00580, or 0 to 0.00573, and C is 0 to 1 × 10 −3 , or 0 to 5.0 × 10 −4 , or 0 to 4.1352 × 10 −4 . Can be satisfied.
また、前記低屈折層に含まれている第2層に対して、楕円偏光法(ellipsometry)で測定した偏極の楕円率を前記一般式1のコーシーモデル(Cauchy model)で最適化(fitting)した時、前記Aは1.0〜1.50、Bは0〜0.007、Cは0〜1×10−3の条件を満足することができ、また、前記低屈折層に含まれている第2層に対して、前記Aは1.10〜1.40、または1.20〜1.35、または1.211〜1.349、かつ、前記Bは0〜0.007、または0〜0.00550、または0〜0.00513、かつ、前記Cは0〜1×10−3、または0〜5.0×10−4、または0〜4.8685×10−4の条件を満足することができる。 In addition, for the second layer included in the low refractive layer, the ellipticity of the polarization measured by elliptic polarization is optimized using the Cauchy model of the general formula 1. When A is 1.0 to 1.50, B is 0 to 0.007, C is 0 to 1 × 10 −3 , and is included in the low refractive layer. And A is 1.10 to 1.40, or 1.20 to 1.35, or 1.211 to 1.349, and B is 0 to 0.007, or 0 with respect to the second layer. -0.00550, or 0-0.00513, and the C satisfies the condition of 0-1 × 10 −3 , 0-5.0 × 10 −4 , or 0-4.885 × 10 −4. can do.
一方、上述した実現例の反射防止フィルムにおいて、前記低屈折層に含まれる第1層と第2層は、異なる範囲の屈折率を有することができる。 On the other hand, in the antireflection film of the implementation example described above, the first layer and the second layer included in the low refractive layer can have different ranges of refractive indexes.
より具体的には、前記低屈折層に含まれる第1層は、550nmにおいて、1.420〜1.600、または1.450〜1.550、または1.480〜1.520、または1.491〜1.511の屈折率を有することができる。また、前記低屈折層に含まれる第2層は、550nmにおいて、1.200〜1.410、または1.210〜1.400、または1.211〜1.375の屈折率を有することができる。 More specifically, the first layer included in the low refractive layer has a thickness of 1.420 to 1.600, or 1.450 to 1.550, or 1.480 to 1.520, or 1.50 nm at 550 nm. It can have a refractive index of 491-1.511. Also, the second layer included in the low refractive layer may have a refractive index of 1.200 to 1.410, or 1.210 to 1.400, or 1.211 to 1.375 at 550 nm. .
上述した屈折率の測定は、通常知られた方法を使用することができ、例えば、前記低屈折層に含まれる第1層と第2層それぞれに対して、380nm〜1,000nmの波長で測定された楕円偏光とCauchyモデルを用いて、550nmにおける屈折率を計算して決定することができる。 For the above-described refractive index measurement, a generally known method can be used. For example, measurement is performed at a wavelength of 380 nm to 1,000 nm with respect to each of the first layer and the second layer included in the low refractive layer. Using the elliptically polarized light and the Cauchy model, the refractive index at 550 nm can be calculated and determined.
一方、前記ソリッド状無機ナノ粒子は、100nm未満の最大直径を有し、その内部に空き空間が存在しない形態の粒子を意味する。 On the other hand, the solid inorganic nanoparticles mean particles having a maximum diameter of less than 100 nm and having no empty space inside.
また、前記中空状無機ナノ粒子は、200nm未満の最大直径を有し、その表面および/または内部に空き空間が存在する形態の粒子を意味する。 The hollow inorganic nanoparticles mean particles having a maximum diameter of less than 200 nm and having a free space on the surface and / or inside thereof.
前記ソリッド状無機ナノ粒子は、0.5〜100nm、または1〜30nmの直径を有することができる。 The solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, or 1 to 30 nm.
前記中空状無機ナノ粒子は、1〜200nm、または10〜100nmの直径を有することができる。 The hollow inorganic nanoparticles may have a diameter of 1 to 200 nm or 10 to 100 nm.
前記ソリッド状無機ナノ粒子および中空状無機ナノ粒子の直径は、粒子断面で確認される最長直径を意味することができる。 The diameters of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may mean the longest diameter confirmed in the particle cross section.
一方、前記ソリッド状無機ナノ粒子および前記中空状無機ナノ粒子それぞれは、表面に(メタ)アクリレート基、エポキシド基、ビニル基(Vinyl)、およびチオール基(Thiol)からなる群より選択された1種以上の反応性官能基を含有することができる。前記ソリッド状無機ナノ粒子および前記中空状無機ナノ粒子それぞれが表面に上述した反応性官能基を含有することによって、前記低屈折層は、より高い架橋度を有することができ、これによって、より向上した耐スクラッチ性および防汚性を確保することができる。 Meanwhile, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles is one selected from the group consisting of (meth) acrylate groups, epoxide groups, vinyl groups (Vinyl), and thiol groups (Thiol) on the surface. The above reactive functional groups can be contained. When the solid inorganic nanoparticle and the hollow inorganic nanoparticle each contain the reactive functional group described above on the surface, the low refractive layer can have a higher degree of cross-linking, thereby improving further. Scratch resistance and antifouling properties can be ensured.
一方、上述した低屈折層は、光重合性化合物、光反応性官能基を含む含フッ素化合物、中空状無機ナノ粒子、ソリッド状無機ナノ粒子、および光開始剤を含む光硬化性コーティング組成物から製造できる。 On the other hand, the above-mentioned low refractive layer is formed from a photocurable coating composition containing a photopolymerizable compound, a fluorine-containing compound containing a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles, and a photoinitiator. Can be manufactured.
これにより、前記低屈折層に含まれるバインダー樹脂は、光重合性化合物の(共)重合体および光反応性官能基を含む含フッ素化合物の間の架橋(共)重合体を含むことができる。 Thereby, the binder resin contained in the low refractive index layer can contain a crosslinked (co) polymer between the (co) polymer of the photopolymerizable compound and the fluorine-containing compound containing the photoreactive functional group.
前記実現例の光硬化性コーティング組成物に含まれる光重合性化合物は、製造される低屈折層のバインダー樹脂の基材を形成することができる。具体的には、前記光重合性化合物は、(メタ)アクリレートまたはビニル基を含む単量体またはオリゴマーを含むことができる。より具体的には、前記光重合性化合物は、(メタ)アクリレートまたはビニル基を1以上、または2以上、または3以上含む単量体またはオリゴマーを含むことができる。 The photopolymerizable compound contained in the photocurable coating composition of the realization example can form a binder resin base material of the low refractive layer to be produced. Specifically, the photopolymerizable compound may include a monomer or oligomer containing (meth) acrylate or a vinyl group. More specifically, the photopolymerizable compound may include a monomer or oligomer containing one or more, or two or more, or three or more (meth) acrylates or vinyl groups.
前記(メタ)アクリレートを含む単量体またはオリゴマーの具体例としては、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールヘプタ(メタ)アクリレート、トリレンジイソシアネート、キシレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンポリエトキシトリ(メタ)アクリレート、トリメチロールプロパントリメタクリレート、エチレングリコールジメタクリレート、ブタンジオールジメタクリレート、ヘキサエチルメタクリレート、ブチルメタクリレート、またはこれらの2種以上の混合物や、またはウレタン変性アクリレートオリゴマー、エポキシドアクリレートオリゴマー、エーテルアクリレートオリゴマー、デンドリティックアクリレートオリゴマー、またはこれらの2種以上の混合物が挙げられる。この時、前記オリゴマーの分子量は、1,000〜10,000であることが好ましい。 Specific examples of the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth). Acrylate, tripentaerythritol hepta (meth) acrylate, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane trimethacrylate, ethylene glycol Dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate Or or a mixture of two or more of these or urethane-modified acrylate oligomer, epoxide acrylate oligomer, ether acrylate oligomers, dendritic acrylate oligomer or a mixture of two or more thereof. At this time, the molecular weight of the oligomer is preferably 1,000 to 10,000.
前記ビニル基を含む単量体またはオリゴマーの具体例としては、ジビニルベンゼン、スチレン、またはパラメチルスチレンが挙げられる。 Specific examples of the monomer or oligomer containing a vinyl group include divinylbenzene, styrene, and paramethylstyrene.
前記光硬化性コーティング組成物中の前記光重合性化合物の含有量が大きく限定されるものではないが、最終的に製造される低屈折層や反射防止フィルムの機械的物性などを考慮して、前記光硬化性コーティング組成物の固形分中の前記光重合性化合物の含有量は、5重量%〜80重量%であってもよい。前記光硬化性コーティング組成物の固形分は、前記光硬化性コーティング組成物中の液状の成分、例えば、後述のように選択的に含まれる有機溶媒などの成分を除いた固体の成分のみを意味する。 Although the content of the photopolymerizable compound in the photocurable coating composition is not greatly limited, considering the mechanical properties of the low refractive layer and antireflection film to be finally produced, The content of the photopolymerizable compound in the solid content of the photocurable coating composition may be 5 wt% to 80 wt%. The solid content of the photocurable coating composition means only a solid component excluding a liquid component in the photocurable coating composition, for example, a component such as an organic solvent selectively contained as described later. To do.
一方、前記光重合性化合物は、上述した単量体またはオリゴマーのほか、フッ素系(メタ)アクリレート系単量体またはオリゴマーをさらに含んでもよい。前記フッ素系(メタ)アクリレート系単量体またはオリゴマーをさらに含む場合、前記(メタ)アクリレートまたはビニル基を含む単量体またはオリゴマーに対する前記フッ素系(メタ)アクリレート系単量体またはオリゴマーの重量比は、0.1%〜10%であってもよい。 On the other hand, the photopolymerizable compound may further contain a fluorine (meth) acrylate monomer or oligomer in addition to the monomer or oligomer described above. When the fluorine-based (meth) acrylate monomer or oligomer is further included, the weight ratio of the fluorine-based (meth) acrylate monomer or oligomer to the monomer or oligomer containing the (meth) acrylate or vinyl group May be 0.1% to 10%.
前記フッ素系(メタ)アクリレート系単量体またはオリゴマーの具体例としては、下記化学式1〜5からなる群より選択される1種以上の化合物が挙げられる。 Specific examples of the fluorine-based (meth) acrylate monomer or oligomer include one or more compounds selected from the group consisting of the following chemical formulas 1 to 5.
前記化学式1において、R1は、水素基または炭素数1〜6のアルキル基であり、aは、0〜7の整数であり、bは、1〜3の整数である。 In the chemical formula 1, R 1 is a hydrogen group or an alkyl group having 1 to 6 carbon atoms, a is an integer of 0 to 7, and b is an integer of 1 to 3.
前記化学式2において、cは、1〜10の整数である。 In the chemical formula 2, c is an integer of 1 to 10.
前記化学式3において、dは、1〜11の整数である。 In Chemical Formula 3, d is an integer of 1 to 11.
前記化学式4において、eは、1〜5の整数である。 In Chemical Formula 4, e is an integer of 1-5.
前記化学式5において、fは、4〜10の整数である。 In Formula 5, f is an integer of 4 to 10.
一方、前記低屈折層には、前記光反応性官能基を含む含フッ素化合物に由来する部分が含まれる。 On the other hand, the low refractive layer includes a portion derived from the fluorine-containing compound containing the photoreactive functional group.
前記光反応性官能基を含む含フッ素化合物には1以上の光反応性官能基が含まれているかまたは置換されていてもよいし、前記光反応性官能基は、光の照射によって、例えば、可視光線または紫外線の照射によって重合反応に参加できる官能基を意味する。前記光反応性官能基は、光の照射によって重合反応に参加できると知られた多様な官能基を含むことができ、その具体例としては、(メタ)アクリレート基、エポキシド基、ビニル基(Vinyl)、またはチオール基(Thiol)が挙げられる。 The fluorine-containing compound containing the photoreactive functional group may contain one or more photoreactive functional groups or may be substituted, and the photoreactive functional group may be irradiated with light, for example, It means a functional group that can participate in a polymerization reaction by irradiation with visible light or ultraviolet light. The photoreactive functional group may include various functional groups known to be able to participate in the polymerization reaction by light irradiation. Specific examples thereof include (meth) acrylate group, epoxide group, vinyl group (Vinyl). ) Or a thiol group (Thiol).
前記光反応性官能基を含む含フッ素化合物それぞれは、2,000〜200,000、好ましくは5,000〜100,000の重量平均分子量(GPC法によって測定したポリスチレン換算の重量平均分子量)を有することができる。 Each of the fluorine-containing compounds containing the photoreactive functional group has a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by GPC method) of 2,000 to 200,000, preferably 5,000 to 100,000. be able to.
前記光反応性官能基を含む含フッ素化合物の重量平均分子量が小さすぎると、前記光硬化性コーティング組成物において、含フッ素化合物が表面に均一で効果的に配列できずに最終的に製造される低屈折層の内部に位置するが、これにより、前記低屈折層の表面が有する防汚性が低下し、前記低屈折層の架橋密度が低くなって、全体的な強度や耐スクラッチ性などの機械的物性が低下することがある。 If the weight-average molecular weight of the fluorine-containing compound containing the photoreactive functional group is too small, the fluorine-containing compound cannot be uniformly and effectively arranged on the surface in the photocurable coating composition and is finally produced. Although located inside the low refractive layer, this reduces the antifouling property of the surface of the low refractive layer, lowers the crosslink density of the low refractive layer, such as overall strength and scratch resistance Mechanical properties may deteriorate.
また、前記光反応性官能基を含む含フッ素化合物の重量平均分子量が高すぎると、前記光硬化性コーティング組成物で他の成分との相溶性が低くなり得、これにより、最終的に製造される低屈折層のヘイズが高くなったり、光透過度が低くなり得、前記低屈折層の強度も低下することがある。 In addition, if the weight-average molecular weight of the fluorine-containing compound containing the photoreactive functional group is too high, the photocurable coating composition may have a low compatibility with other components, thereby being finally produced. The haze of the low refractive layer may increase, the light transmittance may decrease, and the strength of the low refractive layer may also decrease.
具体的には、前記光反応性官能基を含む含フッ素化合物は、i)1つ以上の光反応性官能基が置換され、少なくとも1つの炭素に1以上のフッ素が置換された脂肪族化合物または脂肪族環化合物;ii)1以上の光反応性官能基で置換され、少なくとも1つの水素がフッ素に置換され、1つ以上の炭素がケイ素に置換されたヘテロ(hetero)脂肪族化合物またはヘテロ(hetero)脂肪族環化合物;iii)1つ以上の光反応性官能基が置換され、少なくとも1つのシリコンに1以上のフッ素が置換されたポリジアルキルシロキサン系高分子(例えば、ポリジメチルシロキサン系高分子);iv)1以上の光反応性官能基で置換され、少なくとも1つの水素がフッ素に置換されたポリエーテル化合物、または前記i)〜iv)のうちの2以上の混合物、またはこれらの共重合体が挙げられる。 Specifically, the fluorine-containing compound containing the photoreactive functional group is: i) an aliphatic compound in which one or more photoreactive functional groups are substituted, and at least one carbon is substituted with one or more fluorines; An aliphatic ring compound; ii) a heteroaliphatic compound or hetero (substituted with one or more photoreactive functional groups, wherein at least one hydrogen is replaced with fluorine, and one or more carbons are replaced with silicon hetero) an aliphatic ring compound; iii) a polydialkylsiloxane polymer in which one or more photoreactive functional groups are substituted, and at least one silicon is substituted with one or more fluorines (for example, polydimethylsiloxane polymer) Iv); iv) a polyether compound substituted with one or more photoreactive functional groups and at least one hydrogen substituted with fluorine, or i) to iv) above Mixtures of two or more of, or a copolymer thereof.
前記光硬化性コーティング組成物は、前記光重合性化合物100重量部に対して、前記光反応性官能基を含む含フッ素化合物20〜300重量部を含むことができる。 The photocurable coating composition may include 20 to 300 parts by weight of a fluorine-containing compound containing the photoreactive functional group with respect to 100 parts by weight of the photopolymerizable compound.
前記光重合性化合物対比、前記光反応性官能基を含む含フッ素化合物が過剰に添加される場合、前記実現例の光硬化性コーティング組成物のコーティング性が低下したり、前記光硬化性コーティング組成物から得られた低屈折層が十分な耐久性や耐スクラッチ性を有しないことがある。また、前記光重合性化合物対比、前記光反応性官能基を含む含フッ素化合物の量が小さすぎると、前記光硬化性コーティング組成物から得られた低屈折層が十分な防汚性や耐スクラッチ性などの機械的物性を有しないことがある。 When the fluorine-containing compound containing the photopolymerizable compound and the photoreactive functional group is excessively added, the coating property of the photocurable coating composition of the realization example is lowered, or the photocurable coating composition is used. A low refractive layer obtained from a product may not have sufficient durability and scratch resistance. In addition, if the amount of the fluorine-containing compound containing the photopolymerizable compound and the photoreactive functional group is too small, the low refractive layer obtained from the photocurable coating composition has sufficient antifouling properties and scratch resistance. It may not have mechanical properties such as properties.
前記光反応性官能基を含む含フッ素化合物は、ケイ素またはケイ素化合物をさらに含んでもよい。つまり、前記光反応性官能基を含む含フッ素化合物は、選択的に内部にケイ素またはケイ素化合物を含有することができ、具体的には、前記光反応性官能基を含む含フッ素化合物中のケイ素の含有量は、0.1重量%〜20重量%であってもよい。 The fluorine-containing compound containing the photoreactive functional group may further contain silicon or a silicon compound. That is, the fluorine-containing compound containing the photoreactive functional group can selectively contain silicon or a silicon compound inside, specifically, silicon in the fluorine-containing compound containing the photoreactive functional group. The content of may be 0.1 wt% to 20 wt%.
前記光反応性官能基を含む含フッ素化合物に含まれるケイ素は、前記実現例の光硬化性コーティング組成物に含まれる他の成分との相溶性を高めることができ、これにより、最終的に製造される屈折層にヘイズ(haze)が発生するのを防止して透明度を高める役割を果たすことができる。一方、前記光反応性官能基を含む含フッ素化合物中のケイ素の含有量が大きすぎると、前記光硬化性コーティング組成物に含まれている他の成分と前記含フッ素化合物との間の相溶性がむしろ低下し、これにより、最終的に製造される低屈折層や反射防止フィルムが十分な透光度や反射防止性能を有することができず、表面の防汚性も低下することがある。 Silicon contained in the fluorine-containing compound containing the photoreactive functional group can improve compatibility with other components contained in the photocurable coating composition of the realization example, thereby finally producing It is possible to prevent haze from being generated in the refractive layer and to increase transparency. On the other hand, if the content of silicon in the fluorine-containing compound containing the photoreactive functional group is too large, the compatibility between the fluorine-containing compound and other components contained in the photocurable coating composition However, the low refractive layer and the antireflection film finally produced may not have sufficient translucency and antireflection performance, and the antifouling property of the surface may be lowered.
前記低屈折層は、前記光重合性化合物の(共)重合体100重量部対比、前記中空状無機ナノ粒子10〜400重量部および前記ソリッド状無機ナノ粒子10〜400重量部を含むことができる。 The low refractive layer may include 100 parts by weight of the (co) polymer of the photopolymerizable compound, 10 to 400 parts by weight of the hollow inorganic nanoparticles, and 10 to 400 parts by weight of the solid inorganic nanoparticles. .
前記低屈折層中の前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子の含有量が多すぎる場合、前記低屈折層の製造過程で前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子の間の相分離が十分に起こらずに混在して反射率が高くなり得、表面凹凸が過度に発生して防汚性が低下することがある。また、前記低屈折層中の前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子の含有量が小さすぎる場合、前記ハードコート層および前記低屈折層の間の界面から近い領域に前記ソリッド状無機ナノ粒子中の多数が位置しにくいことがあり、前記低屈折層の反射率は非常に高くなり得る。 When the content of the hollow inorganic nanoparticles and solid inorganic nanoparticles in the low refractive layer is too large, the phase between the hollow inorganic nanoparticles and solid inorganic nanoparticles in the manufacturing process of the low refractive layer Separation may not occur sufficiently and may be mixed to increase the reflectance, resulting in excessive surface irregularities and reduced antifouling properties. Further, when the content of the hollow inorganic nanoparticle and the solid inorganic nanoparticle in the low refractive layer is too small, the solid inorganic nanoparticle is in a region near the interface between the hard coat layer and the low refractive layer. Many of the particles may be difficult to locate and the reflectivity of the low refractive layer can be very high.
前記低屈折層は、1nm〜300nm、または50nm〜200nm、または85nm〜300nmの厚さを有することができる。 The low refractive layer may have a thickness of 1 nm to 300 nm, or 50 nm to 200 nm, or 85 nm to 300 nm.
一方、前記ハードコート層としては、通常知られたハードコート層を大きな制限なく使用することができる。 On the other hand, as the hard coat layer, a conventionally known hard coat layer can be used without any major limitation.
前記ハードコート層の一例として、光硬化性樹脂を含むバインダー樹脂および前記バインダー樹脂に分散した有機または無機微粒子;を含むハードコート層が挙げられる。 An example of the hard coat layer is a hard coat layer containing a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin.
前記ハードコート層に含まれる光硬化型樹脂は、紫外線などの光が照射されると、重合反応を起こし得る光硬化型化合物の重合体であって、当業界における通常のものであってもよい。具体的には、前記光硬化性樹脂は、ウレタンアクリレートオリゴマー、エポキシドアクリレートオリゴマー、ポリエステルアクリレート、およびポリエーテルアクリレートからなる反応性アクリレートオリゴマー群;およびジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヒドロキシペンタアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリアクリレート、トリメチレンプロピルトリアクリレート、プロポキシル化グリセロールトリアクリレート、トリメチルプロパンエトキシトリアクリレート、1,6−ヘキサンジオールジアクリレート、プロポキシル化グリセロトリアクリレート、トリプロピレングリコールジアクリレート、およびエチレングリコールジアクリレートからなる多官能性アクリレート単量体群より選択される1種以上を含むことができる。 The photocurable resin contained in the hard coat layer is a polymer of a photocurable compound capable of causing a polymerization reaction when irradiated with light such as ultraviolet rays, and may be a normal one in the industry. . Specifically, the photocurable resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; and dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, penta Erythritol tetraacrylate, pentaerythritol triacrylate, trimethylenepropyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxytriacrylate, 1,6-hexanediol diacrylate, propoxylated glycerotriacrylate, tripropylene glycol diacrylate, And consisting of ethylene glycol diacrylate It may include one or more selected from potentially acrylate monomer group.
前記有機または無機微粒子は、粒径が具体的に限定されるものではないが、例えば、有機微粒子は、1〜10μmの粒径を有し、前記無機粒子は、1nm〜500nm、または1nm〜300nmの粒径を有することができる。前記有機または無機微粒子の粒径は、体積平均粒径で定義される。 The organic or inorganic fine particles are not specifically limited in particle size. For example, the organic fine particles have a particle size of 1 to 10 μm, and the inorganic particles have a particle size of 1 nm to 500 nm, or 1 nm to 300 nm. Can have a particle size of The particle diameter of the organic or inorganic fine particles is defined by a volume average particle diameter.
また、前記ハードコートフィルムに含まれる有機または無機微粒子の具体例が限定されるものではないが、例えば、前記有機または無機微粒子は、アクリル系樹脂、スチレン系樹脂、エポキシド樹脂、およびナイロン樹脂からなる有機微粒子であるか、酸化ケイ素、二酸化チタン、酸化インジウム、酸化スズ、酸化ジルコニウム、および酸化亜鉛からなる無機微粒子であってもよい。 Further, specific examples of the organic or inorganic fine particles contained in the hard coat film are not limited. For example, the organic or inorganic fine particles are made of acrylic resin, styrene resin, epoxide resin, and nylon resin. It may be organic fine particles or inorganic fine particles made of silicon oxide, titanium dioxide, indium oxide, tin oxide, zirconium oxide, and zinc oxide.
前記ハードコート層のバインダー樹脂は、重量平均分子量10,000以上の高分子量(共)重合体をさらに含んでもよい。 The binder resin of the hard coat layer may further include a high molecular weight (co) polymer having a weight average molecular weight of 10,000 or more.
前記高分子量(共)重合体は、セルロース系ポリマー、アクリル系ポリマー、スチレン系ポリマー、エポキシド系ポリマー、ナイロン系ポリマー、ウレタン系ポリマー、およびポリオレフィン系ポリマーからなる群より選択される1種以上であってもよい。 The high molecular weight (co) polymer is at least one selected from the group consisting of a cellulose polymer, an acrylic polymer, a styrene polymer, an epoxide polymer, a nylon polymer, a urethane polymer, and a polyolefin polymer. May be.
一方、前記ハードコートフィルムの他の例として、光硬化性樹脂のバインダー樹脂;および前記バインダー樹脂に分散した帯電防止剤を含むハードコートフィルムが挙げられる。 On the other hand, as another example of the hard coat film, a hard coat film containing a binder resin of a photocurable resin; and an antistatic agent dispersed in the binder resin can be given.
前記ハードコート層に含まれる光硬化型樹脂は、紫外線などの光が照射されると、重合反応を起こし得る光硬化型化合物の重合体であって、当業界における通常のものであってもよい。ただし、好ましくは、前記光硬化型化合物は、多官能性(メタ)アクリレート系単量体またはオリゴマーであってもよく、この時、(メタ)アクリレート系官能基の数は2〜10、好ましくは2〜8、より好ましくは2〜7であるのが、ハードコート層の物性確保の側面で有利である。より好ましくは、前記光硬化型化合物は、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールヘプタ(メタ)アクリレート、トリペンタエリスリトールヘプタ(メタ)アクリレート、トリレンジイソシアネート、キシレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチロールプロパントリ(メタ)アクリレート、およびトリメチロールプロパンポリエトキシトリ(メタ)アクリレートからなる群より選択される1種以上であってもよい。 The photocurable resin contained in the hard coat layer is a polymer of a photocurable compound capable of causing a polymerization reaction when irradiated with light such as ultraviolet rays, and may be a normal one in the industry. . However, preferably, the photocurable compound may be a polyfunctional (meth) acrylate monomer or oligomer, wherein the number of (meth) acrylate functional groups is 2 to 10, preferably 2-8, more preferably 2-7 is advantageous in terms of securing the physical properties of the hard coat layer. More preferably, the photocurable compound is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hepta ( Selected from the group consisting of (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane polyethoxytri (meth) acrylate 1 or more types may be sufficient.
前記帯電防止剤は、4級アンモニウム塩化合物;ピリジニウム塩;1〜3個のアミノ基を有する陽イオン性化合物;スルホン酸塩基、硫酸エステル塩基、リン酸エステル塩基、ホスホン酸塩基などの陰イオン性化合物;アミノ酸系またはアミノ硫酸エステル系化合物などの両性化合物;イミノアルコール系化合物、グリセリン系化合物、ポリエチレングリコール系化合物などの非イオン性化合物;スズまたはチタンなどを含む金属アルコキシド化合物などの有機金属化合物;前記有機金属化合物のアセチルアセトナート塩などの金属キレート化合物;これら化合物の2種以上の反応物または高分子化物;これら化合物の2種以上の混合物であってもよい。ここで、前記4級アンモニウム塩化合物は、分子内に1個以上の4級アンモニウム塩基を有する化合物であってもよいし、低分子型または高分子型を制限なく使用することができる。 The antistatic agent includes a quaternary ammonium salt compound; a pyridinium salt; a cationic compound having 1 to 3 amino groups; anionic properties such as a sulfonate group, a sulfate ester base, a phosphate ester base, and a phosphonate base. Compounds; amphoteric compounds such as amino acid or aminosulfate compounds; nonionic compounds such as imino alcohol compounds, glycerin compounds, polyethylene glycol compounds; organometallic compounds such as metal alkoxide compounds including tin or titanium; It may be a metal chelate compound such as an acetylacetonate salt of the organometallic compound; two or more reactants or polymerized products of these compounds; a mixture of two or more of these compounds. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium bases in the molecule, and a low molecular type or a high molecular type can be used without limitation.
また、前記帯電防止剤としては、導電性高分子と金属酸化物微粒子も使用可能である。前記導電性高分子としては、芳香族共役系ポリ(パラフェニレン)、ヘテロ環式共役系のポリピロール、ポリチオフェン、脂肪族共役系のポリアセチレン、ヘテロ原子を含む共役系のポリアニリン、混合型共役系のポリ(フェニレンビニレン)、分子中に複数の共役鎖を有する共役系の複鎖状共役系化合物、共役高分子鎖を飽和高分子にグラフトまたはブロック共重合させた導電性複合体などがある。さらに、前記金属酸化物微粒子としては、酸化亜鉛、酸化アンチモン、酸化スズ、酸化セリウム、インジウムスズ酸化物、酸化インジウム、酸化アルミニウム、アンチモンドーピングされた酸化スズ、アルミニウムドーピングされた酸化亜鉛などが挙げられる。 As the antistatic agent, conductive polymer and metal oxide fine particles can also be used. Examples of the conductive polymer include aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, conjugated polyaniline containing a hetero atom, and mixed conjugated poly. (Phenylene vinylene), conjugated double-chain conjugated compounds having a plurality of conjugated chains in the molecule, and conductive composites obtained by grafting or block copolymerizing conjugated polymer chains onto saturated polymers. Furthermore, examples of the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminum oxide, antimony-doped tin oxide, and aluminum-doped zinc oxide. .
前記光硬化性樹脂のバインダー樹脂;および前記バインダー樹脂に分散した帯電防止剤を含むハードコートフィルムは、アルコキシシラン系オリゴマーおよび金属アルコキシド系オリゴマーからなる群より選択される1種以上の化合物をさらに含んでもよい。 The hard coat film containing a binder resin of the photocurable resin; and an antistatic agent dispersed in the binder resin further includes one or more compounds selected from the group consisting of an alkoxysilane oligomer and a metal alkoxide oligomer. But you can.
前記アルコキシシラン系化合物は、当業界における通常のものであってもよいが、好ましくは、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン、グリシドキシプロピルトリメトキシシラン、およびグリシドキシプロピルトリエトキシシランからなる群より選択される1種以上の化合物であってもよい。 The alkoxysilane compound may be a normal compound in the industry, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyltrimethyl. It may be one or more compounds selected from the group consisting of methoxysilane, glycidoxypropyltrimethoxysilane, and glycidoxypropyltriethoxysilane.
また、前記金属アルコキシド系オリゴマーは、金属アルコキシド系化合物および水を含む組成物のゾル−ゲル反応により製造することができる。前記ゾル−ゲル反応は、上述したアルコキシシラン系オリゴマーの製造方法に準ずる方法で行うことができる。 The metal alkoxide oligomer can be produced by a sol-gel reaction of a composition containing a metal alkoxide compound and water. The sol-gel reaction can be carried out by a method according to the above-described method for producing an alkoxysilane oligomer.
ただし、前記金属アルコキシド系化合物は、水と急激に反応し得るため、前記金属アルコキシド系化合物を有機溶媒に希釈した後、水をゆっくりドロップする方法で前記ゾル−ゲル反応を行うことができる。この時、反応効率などを勘案して、水に対する金属アルコキシド化合物のモル比(金属イオン基準)は、3〜170の範囲内で調節することが好ましい。 However, since the metal alkoxide compound can react rapidly with water, the sol-gel reaction can be performed by slowly dropping water after the metal alkoxide compound is diluted in an organic solvent. At this time, it is preferable to adjust the molar ratio of the metal alkoxide compound to water (based on the metal ion) within a range of 3 to 170 in consideration of the reaction efficiency and the like.
ここで、前記金属アルコキシド系化合物は、チタンテトラ−イソプロポキシド、ジルコニウムイソプロポキシド、およびアルミニウムイソプロポキシドからなる群より選択される1種以上の化合物であってもよい。 Here, the metal alkoxide compound may be one or more compounds selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide, and aluminum isopropoxide.
前記ハードコート層は、0.1μm〜100μmの厚さを有することができる。 The hard coat layer may have a thickness of 0.1 μm to 100 μm.
前記ハードコート層の他の一面に結合された基材をさらに含んでもよい。前記基材の具体的な種類や厚さは大きく限定されるものではなく、低屈折層または反射防止フィルムの製造に使用されると知られた基材を大きな制限なく使用することができる。 A substrate bonded to the other surface of the hard coat layer may be further included. The specific kind and thickness of the base material are not greatly limited, and a base material known to be used for the production of a low refractive layer or an antireflection film can be used without any major limitation.
一方、前記実現例の反射防止フィルムは、光硬化型化合物またはその(共)重合体、光反応性官能基を含む含フッ素化合物、光開始剤、中空状無機ナノ粒子およびソリッド状無機ナノ粒子を含む低屈折層形成用樹脂組成物をハードコート層上に塗布し、35℃〜100℃の温度で乾燥する段階;および前記樹脂組成物の乾燥物を光硬化する段階;を含む反射防止フィルムの製造方法により提供できる。 On the other hand, the antireflection film of the realization example includes a photocurable compound or a (co) polymer thereof, a fluorine-containing compound containing a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and solid inorganic nanoparticles. An antireflective film comprising: a step of applying a resin composition for forming a low refractive layer on a hard coat layer and drying at a temperature of 35 ° C. to 100 ° C .; and photocuring the dried product of the resin composition. It can be provided by a manufacturing method.
具体的には、前記反射防止フィルムの製造方法により提供される反射防止フィルムは、低屈折層内で中空状無機ナノ粒子およびソリッド状無機ナノ粒子が互いに区分可能に分布させ、これにより、低い反射率および高い透光率を有しかつ、高い耐スクラッチ性および防汚性を同時に実現することができる。 Specifically, the antireflection film provided by the method for producing an antireflection film distributes hollow inorganic nanoparticles and solid inorganic nanoparticles in a low refractive layer so as to be distinguishable from each other, thereby reducing low reflection. High scratch resistance and antifouling properties can be realized at the same time.
より詳しくは、前記反射防止フィルムは、ハードコート層;および前記ハードコート層の一面に形成され、バインダー樹脂と前記バインダー樹脂に分散した中空状無機ナノ粒子およびソリッド状無機ナノ粒子を含む低屈折層;を含み、前記ハードコート層および前記低屈折層の間の界面から前記低屈折層全体厚さの50%以内に前記ソリッド状無機ナノ粒子全体中の70体積%以上が存在し得る。 More specifically, the antireflective film comprises a hard coat layer; and a low refractive layer formed on one surface of the hard coat layer and comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin. 70% by volume or more in the entire solid inorganic nanoparticles may be present within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.
また、前記中空状無機ナノ粒子全体中の30体積%以上が、前記ソリッド状無機ナノ粒子全体より、前記ハードコート層および前記低屈折層の間の界面から前記低屈折層の厚さ方向により遠い距離に存在し得る。 Further, 30% by volume or more in the whole hollow inorganic nanoparticles is farther from the interface between the hard coat layer and the low refractive layer than the whole solid inorganic nanoparticles in the thickness direction of the low refractive layer. Can exist at a distance.
さらに、前記ハードコート層と前記低屈折層との界面から前記低屈折層全体厚さの30%以内に前記ソリッド状無機ナノ粒子全体中の70体積%以上が存在し得る。また、前記ハードコート層と前記低屈折層との界面から前記低屈折層全体厚さの30%超過の領域に前記中空状無機ナノ粒子全体中の70体積%以上が存在し得る。 Further, 70% by volume or more of the entire solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. Further, 70% by volume or more of the whole hollow inorganic nanoparticles may be present in a region exceeding 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.
さらに、前記反射防止フィルムの製造方法により提供される反射防止フィルムにおいて、前記低屈折層は、前記ソリッド状無機ナノ粒子全体中の70重量%以上が含まれている第1層と、前記中空状無機ナノ粒子全体中の70重量%以上が含まれている第2層とを含むことができ、前記第1層が、第2層に比べて、前記ハードコート層および前記低屈折層の間の界面により近く位置し得る。 Further, in the antireflection film provided by the method for producing an antireflection film, the low refractive layer includes a first layer containing 70% by weight or more of the whole solid inorganic nanoparticles, and the hollow shape. A second layer including 70% by weight or more of the entire inorganic nanoparticles, and the first layer is between the hard coat layer and the low refractive layer compared to the second layer. It can be located closer to the interface.
前記低屈折層は、光硬化型化合物またはその(共)重合体、光反応性官能基を含む含フッ素化合物、光開始剤、中空状無機ナノ粒子およびソリッド状無機ナノ粒子を含む低屈折層形成用樹脂組成物をハードコート層上に塗布し、35℃〜100℃、または40℃〜80℃の温度で乾燥することにより形成される。 The low-refractive layer is formed of a low-refractive layer including a photocurable compound or a (co) polymer thereof, a fluorine-containing compound containing a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and solid inorganic nanoparticles. The resin composition is applied on the hard coat layer and dried at a temperature of 35 ° C to 100 ° C or 40 ° C to 80 ° C.
前記ハードコート層上に塗布された低屈折層形成用樹脂組成物を乾燥する温度が35℃未満であれば、前記形成される低屈折層の有する防汚性が大きく低下することがある。また、前記ハードコート層上に塗布された低屈折層形成用樹脂組成物を乾燥する温度が100℃超過であれば、前記低屈折層の製造過程で前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子の間の相分離が十分に起こらずに混在して、前記低屈折層の耐スクラッチ性および防汚性が低下するだけでなく、反射率も非常に高くなり得る。 If the temperature for drying the resin composition for forming a low refractive layer applied on the hard coat layer is less than 35 ° C., the antifouling property of the formed low refractive layer may be greatly reduced. In addition, if the temperature for drying the resin composition for forming a low refractive layer applied on the hard coat layer exceeds 100 ° C., the hollow inorganic nanoparticles and the solid inorganic nanoparticles are produced during the manufacturing process of the low refractive layer. Not only does the phase separation between the particles not occur sufficiently, but the low refractive layer not only deteriorates scratch resistance and antifouling properties, but also has a very high reflectance.
前記ハードコート層上に塗布された低屈折層形成用樹脂組成物を乾燥する過程で、前記乾燥温度と共に前記ソリッド状無機ナノ粒子および中空状無機ナノ粒子の間の密度の差を調節することによって、上述した特性を有する低屈折層を形成することができる。前記ソリッド状無機ナノ粒子が、前記中空状無機ナノ粒子に比べて0.50g/cm3以上高い密度を有することができ、このような密度の差によって、前記ハードコート層上に形成される低屈折層で前記ソリッド状無機ナノ粒子がハードコート層側により近い側に位置し得る。 In the process of drying the resin composition for forming a low refractive layer applied on the hard coat layer, by adjusting the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles together with the drying temperature. A low refractive layer having the above-described characteristics can be formed. The solid inorganic nanoparticles may have a density higher by 0.50 g / cm 3 or more than the hollow inorganic nanoparticles, and the low density formed on the hard coat layer due to the difference in density. In the refractive layer, the solid inorganic nanoparticles may be located closer to the hard coat layer side.
具体的には、前記ソリッド状無機ナノ粒子は、2.00g/cm3〜4.00g/cm3の密度を有し、前記中空状無機ナノ粒子は、1.50g/cm3〜3.50g/cm3の密度を有することができる。 Specifically, the solid-like inorganic nanoparticles have a density of 2.00g / cm 3 ~4.00g / cm 3 , the hollow inorganic nanoparticles, 1.50g / cm 3 ~3.50g / Cm 3 density.
一方、前記ハードコート層上に塗布された低屈折層形成用樹脂組成物を35℃〜100℃の温度で乾燥する段階は、10秒〜5分間、または30秒〜4分間行われる。 On the other hand, the step of drying the resin composition for forming a low refractive layer applied on the hard coat layer at a temperature of 35 ° C. to 100 ° C. is performed for 10 seconds to 5 minutes, or 30 seconds to 4 minutes.
前記乾燥時間が短すぎる場合、上述した前記ソリッド状無機ナノ粒子および中空状無機ナノ粒子の間の相分離現象が十分に起こらないことがある。これに対し、前記乾燥時間が長すぎる場合、前記形成される低屈折層がハードコート層を侵食し得る。 When the drying time is too short, the phase separation phenomenon between the solid inorganic nanoparticles and the hollow inorganic nanoparticles described above may not occur sufficiently. On the other hand, when the drying time is too long, the formed low refractive layer can erode the hard coat layer.
一方、前記低屈折層は、光硬化型化合物またはその(共)重合体、光反応性官能基を含む含フッ素化合物、中空状無機ナノ粒子、ソリッド状無機ナノ粒子、および光開始剤を含む光硬化性コーティング組成物から製造できる。 On the other hand, the low refractive layer is a light containing a photocurable compound or a (co) polymer thereof, a fluorine-containing compound containing a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles, and a photoinitiator. It can be produced from a curable coating composition.
前記低屈折層は、前記光硬化性コーティング組成物を所定の基材上に塗布し、塗布された結果物を光硬化することにより得られる。前記基材の具体的な種類や厚さは大きく限定されるものではなく、低屈折層または反射防止フィルムの製造に使用されると知られた基材を大きな制限なく使用することができる。 The low refractive layer is obtained by applying the photocurable coating composition on a predetermined substrate and photocuring the applied result. The specific kind and thickness of the base material are not greatly limited, and a base material known to be used for the production of a low refractive layer or an antireflection film can be used without any major limitation.
前記光硬化性コーティング組成物を塗布するのに通常使用される方法および装置を格別な制限なく使用可能であり、例えば、Meyer barなどのバーコーティング法、グラビアコーティング法、2roll reverseコーティング法、vacuum slot dieコーティング法、2rollコーティング法などを使用することができる。 The method and apparatus normally used for applying the photocurable coating composition can be used without any particular limitation, for example, bar coating method such as Meyer bar, gravure coating method, 2 roll reverse coating method, vacuum slot. A die coating method, a 2 roll coating method, or the like can be used.
前記低屈折層は、1nm〜300nm、または50nm〜200nmの厚さを有することができる。これにより、前記所定の基材上に塗布される前記光硬化性コーティング組成物の厚さは、約1nm〜300nm、または50nm〜200nmであってもよい。 The low refractive layer may have a thickness of 1 nm to 300 nm, or 50 nm to 200 nm. Accordingly, the thickness of the photocurable coating composition applied on the predetermined substrate may be about 1 nm to 300 nm, or 50 nm to 200 nm.
前記光硬化性コーティング組成物を光硬化させる段階では、200〜400nmの波長の紫外線または可視光線を照射することができ、照射時の露光量は100〜4,000mJ/cm2が好ましい。露光時間も特に限定されるものではなく、使用される露光装置、照射光線の波長または露光量に応じて適宜変化させることができる。 In the step of photocuring the photocurable coating composition, can be irradiated with ultraviolet or visible light having a wavelength of 200 to 400 nm, exposure amount at the time of irradiation is preferably 100~4,000mJ / cm 2. The exposure time is also not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiation light, or the exposure amount.
また、前記光硬化性コーティング組成物を光硬化させる段階では、窒素大気条件を適用するために、窒素パージングなどを行うことができる。 Further, in the step of photocuring the photocurable coating composition, nitrogen purging or the like can be performed in order to apply nitrogen atmospheric conditions.
前記光硬化型化合物、中空状無機ナノ粒子、ソリッド状無機ナノ粒子、および光反応性官能基を含む含フッ素化合物に関する具体的な内容は、前記一実現例の反射防止フィルムに関して上述した内容を含む。 Specific contents regarding the photocurable compound, the hollow inorganic nanoparticles, the solid inorganic nanoparticles, and the fluorine-containing compound containing the photoreactive functional group include the contents described above with respect to the antireflection film of the one implementation example. .
前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子それぞれは、所定の分散媒に分散したコロイド状に組成物に含まれる。前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子を含むそれぞれのコロイド状は、分散媒として有機溶媒を含むことができる。 Each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles is included in the composition in a colloidal form dispersed in a predetermined dispersion medium. Each colloidal shape including the hollow inorganic nanoparticles and the solid inorganic nanoparticles may include an organic solvent as a dispersion medium.
前記光硬化性コーティング組成物中の前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子それぞれの含有量範囲や前記光硬化性コーティング組成物の粘度などを考慮して、前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子それぞれのコロイド状中の含有量が決定可能であり、例えば、前記コロイド状中の前記中空状無機ナノ粒子およびソリッド状無機ナノ粒子それぞれの固形分含有量は、5重量%〜60重量%であってもよい。 In consideration of the content range of each of the hollow inorganic nanoparticles and solid inorganic nanoparticles in the photocurable coating composition and the viscosity of the photocurable coating composition, the hollow inorganic nanoparticles and the solid The colloidal content of each of the inorganic inorganic nanoparticles can be determined. For example, the solid content of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the colloidal state is 5% by weight to 60%. It may be weight percent.
ここで、前記分散媒中の有機溶媒としては、メタノール、イソプロピルアルコール、エチレングリコール、ブタノールなどのアルコール類;メチルエチルケトン、メチルイソブチルケトンなどのケトン類;トルエン、キシレンなどの芳香族炭化水素類;ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドンなどのアミド類;酢酸エチル、酢酸ブチル、ガンマブチロラクトンなどのエステル類;テトラヒドロフラン、1,4−ジオキサンなどのエーテル類;またはこれらの混合物が含まれる。 Here, examples of the organic solvent in the dispersion medium include alcohols such as methanol, isopropyl alcohol, ethylene glycol and butanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide Amides such as dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and gamma butyrolactone; ethers such as tetrahydrofuran and 1,4-dioxane; or a mixture thereof.
前記光重合開始剤としては、光硬化性樹脂組成物に使用できると知られた化合物であれば大きな制限なく使用可能であり、具体的には、ベンゾフェノン系化合物、アセトフェノン系化合物、ビイミダゾール系化合物、トリアジン系化合物、オキシム系化合物、またはこれらの2種以上の混合物を使用することができる。 As the photopolymerization initiator, any compound known to be usable in a photocurable resin composition can be used without any major limitation. Specifically, a benzophenone compound, an acetophenone compound, a biimidazole compound can be used. , Triazine compounds, oxime compounds, or a mixture of two or more thereof.
前記光重合性化合物100重量部に対して、前記光重合開始剤は1〜100重量部の含有量で使用できる。前記光重合開始剤の量が小さすぎると、前記光硬化性コーティング組成物の光硬化段階で未硬化残留する物質が発生することがある。前記光重合開始剤の量が多すぎると、未反応開始剤が不純物として残留したり、架橋密度が低くなって、製造されるフィルムの機械的物性が低下したり、反射率が非常に高くなり得る。 The photopolymerization initiator can be used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the photopolymerizable compound. If the amount of the photopolymerization initiator is too small, a material that remains uncured in the photocuring stage of the photocurable coating composition may be generated. If the amount of the photopolymerization initiator is too large, the unreacted initiator remains as an impurity, the crosslink density is lowered, the mechanical properties of the produced film are lowered, and the reflectance becomes very high. obtain.
一方、前記光硬化性コーティング組成物は、有機溶媒をさらに含んでもよい。 Meanwhile, the photocurable coating composition may further include an organic solvent.
前記有機溶媒の非制限的な例を挙げると、ケトン類、アルコール類、アセテート類およびエーテル類、またはこれらの2種以上の混合物が挙げられる。 Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, or a mixture of two or more thereof.
このような有機溶媒の具体例としては、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、またはイソブチルケトンなどのケトン類;メタノール、エタノール、ジアセトンアルコール、n−プロパノール、i−プロパノール、n−ブタノール、i−ブタノール、またはt−ブタノールなどのアルコール類;エチルアセテート、i−プロピルアセテート、またはポリエチレングリコールモノメチルエーテルアセテートなどのアセテート類;テトラヒドロフランまたはプロピレングリコールモノメチルエーテルなどのエーテル類;またはこれらの2種以上の混合物が挙げられる。 Specific examples of such organic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, or isobutyl ketone; methanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol, i-butanol. Or alcohols such as t-butanol; acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; ethers such as tetrahydrofuran or propylene glycol monomethyl ether; or mixtures of two or more thereof It is done.
前記有機溶媒は、前記光硬化性コーティング組成物に含まれる各成分を混合する時期に添加されるか、各成分が有機溶媒に分散または混合された状態で添加されることによって、前記光硬化性コーティング組成物に含まれる。前記光硬化性コーティング組成物中の有機溶媒の含有量が小さすぎると、前記光硬化性コーティング組成物の流れ性が低下して、最終的に製造されるフィルムに縞模様が生じるなどの不良が発生することがある。また、前記有機溶媒の過剰添加時、固形分含有量が低くなって、コーティングおよび成膜が十分でなくてフィルムの物性や表面特性が低下し、乾燥および硬化過程で不良が発生することがある。これにより、前記光硬化性コーティング組成物は、含まれる成分の全体固形分の濃度が1重量%〜50重量%、または2〜20重量%となるように有機溶媒を含むことができる。 The organic solvent is added at the time of mixing each component contained in the photocurable coating composition, or is added in a state where each component is dispersed or mixed in the organic solvent, whereby the photocurable composition is added. Included in the coating composition. If the content of the organic solvent in the photocurable coating composition is too small, the flowability of the photocurable coating composition is reduced, and defects such as stripes appear in the finally produced film. May occur. In addition, when the organic solvent is excessively added, the solid content is low, coating and film formation are not sufficient, the physical properties and surface characteristics of the film are lowered, and defects may occur in the drying and curing processes. . Thereby, the said photocurable coating composition can contain an organic solvent so that the density | concentration of the total solid of the component contained may be 1 to 50 weight% or 2 to 20 weight%.
前記ハードコート層は、反射防止フィルムに使用できると知られた材質であれば大きな制限なく使用可能である。 The hard coat layer can be used without any major limitation as long as it is a material known to be usable for an antireflection film.
具体的には、前記反射防止フィルムの製造方法は、光硬化型化合物またはその(共)重合体、光開始剤、および帯電防止剤を含むハードコート層形成用高分子樹脂組成物を基材上に塗布し、光硬化する段階をさらに含んでもよいし、前記段階によりハードコート層を形成することができる。 Specifically, the production method of the antireflection film includes a photopolymerizable compound or a (co) polymer thereof, a photoinitiator, and a polymer resin composition for forming a hard coat layer containing an antistatic agent on a substrate. The method may further include a step of applying and photocuring, and a hard coat layer may be formed by the step.
前記ハードコート層の形成に使用される成分に関しては、前記一実現例の反射防止フィルムに関して上述した通りである。 The components used for forming the hard coat layer are as described above with respect to the antireflection film of the one realization example.
また、前記ハードコート層形成用高分子樹脂組成物は、アルコキシシラン系オリゴマーおよび金属アルコキシド系オリゴマーからなる群より選択される1種以上の化合物をさらに含んでもよい。 The polymer resin composition for forming a hard coat layer may further contain one or more compounds selected from the group consisting of alkoxysilane oligomers and metal alkoxide oligomers.
前記ハードコート層形成用高分子樹脂組成物を塗布するのに通常使用される方法および装置を格別な制限なく使用可能であり、例えば、Meyer barなどのバーコーティング法、グラビアコーティング法、2roll reverseコーティング法、vacuum slot dieコーティング法、2rollコーティング法などを使用することができる。 The method and apparatus normally used for applying the polymer resin composition for forming the hard coat layer can be used without any particular limitation. For example, bar coating method such as Meyer bar, gravure coating method, 2 roll reverse coating Method, vacuum slot die coating method, 2 roll coating method and the like can be used.
前記ハードコート層形成用高分子樹脂組成物を光硬化させる段階では、200〜400nmの波長の紫外線または可視光線を照射することができ、照射時の露光量は100〜4,000mJ/cm2が好ましい。露光時間も特に限定されるものではなく、使用される露光装置、照射光線の波長または露光量に応じて適宜変化させることができる。また、前記ハードコート層形成用高分子樹脂組成物を光硬化させる段階では、窒素大気条件を適用するために、窒素パージングなどを行うことができる。 In the step of photocuring the polymer resin composition for forming a hard coat layer, ultraviolet rays or visible rays having a wavelength of 200 to 400 nm can be irradiated, and the exposure amount at the time of irradiation is 100 to 4,000 mJ / cm 2. preferable. The exposure time is also not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiation light, or the exposure amount. In addition, in the step of photocuring the polymer resin composition for forming a hard coat layer, nitrogen purging or the like can be performed in order to apply nitrogen atmospheric conditions.
本発明によれば、低い反射率および高い透光率を有しかつ、高い耐スクラッチ性および防汚性を同時に実現することができ、ディスプレイ装置の画面の鮮明度を高めることができる反射防止フィルムおよび前記反射防止フィルムの製造方法が提供可能である。 According to the present invention, an antireflection film that has a low reflectance and a high light transmittance, can simultaneously realize high scratch resistance and antifouling properties, and can improve the clarity of the screen of a display device. And the manufacturing method of the said antireflection film can be provided.
発明を下記の実施例でより詳細に説明する。ただし、下記の実施例は本発明を例示するものに過ぎず、本発明の内容が下記の実施例によって限定されるものではない。 The invention is explained in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited by the following examples.
<製造例>
製造例:ハードコートフィルムの製造
KYOEISHA社の塩タイプの帯電防止ハードコート液(固形分50重量%、製品名:LJD−1000)をトリアセチルセルロースフィルムに#10mayer barでコーティングし、90℃で1分間乾燥した後、150mJ/cm2の紫外線を照射して、約5〜6μmの厚さを有するハードコートフィルムを製造した。
<Production example>
Production Example: Production of Hard Coat Film A salt type antistatic hard coat solution (solid content 50% by weight, product name: LJD-1000) manufactured by KYOEISHA was coated on a triacetyl cellulose film with # 10 mayer bar, and 1 at 90 ° C. After drying for a minute, 150 mJ / cm 2 ultraviolet rays were irradiated to produce a hard coat film having a thickness of about 5 to 6 μm.
<実施例1〜5:反射防止フィルムの製造>
実施例1〜4
(1)低屈折層製造用光硬化性コーティング組成物の製造
ペンタエリスリトールトリアクリレート(PETA)100重量部に対して、中空状シリカナノ粒子(直径:約50〜60nm、密度:1.96g/cm3、JSC catalyst and chemicals社製品)281重量部、ソリッド状シリカナノ粒子(直径:約12nm、密度:2.65g/cm3)63重量部、第1含フッ素化合物(X−71−1203M、ShinEtsu社)131重量部、第2含フッ素化合物(RS−537、DIC社)19重量部、開始剤(Irgacure127、Ciba社)31重量部を、MIBK(methyl isobutyl ketone)溶媒に固形分濃度3重量%となるように希釈した。
<Examples 1 to 5: Production of antireflection film>
Examples 1-4
(1) Production of photocurable coating composition for producing low refractive layer Hollow silica nanoparticles (diameter: about 50-60 nm, density: 1.96 g / cm 3 ) with respect to 100 parts by weight of pentaerythritol triacrylate (PETA). , JSC catalyst and chemicals) 281 parts by weight, solid silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cm 3 ) 63 parts by weight, first fluorine-containing compound (X-71-1203M, ShinEtsu) 131 parts by weight, second fluorine-containing compound (RS-537, DIC) 19 parts by weight, initiator (Irgacure 127, Ciba) 31 parts by weight in a solid isobutyl ketone (MIBK) solvent having a solid content concentration of 3% by weight. Diluted.
(2)低屈折層および反射防止フィルムの製造
前記製造例のハードコートフィルム上に、前記得られた光硬化性コーティング組成物を#4mayer barで厚さが約110〜120nmとなるようにコーティングし、下記表1の温度および時間で乾燥および硬化した。前記硬化時には、窒素パージング下、前記乾燥したコーティング物に252mJ/cm2の紫外線を照射した。
(2) Production of Low Refractive Layer and Antireflection Film On the hard coat film of the production example, the obtained photocurable coating composition was coated with # 4mayer bar so that the thickness was about 110 to 120 nm. These were dried and cured at the temperatures and times shown in Table 1 below. During the curing, the dried coating was irradiated with 252 mJ / cm 2 of ultraviolet light under nitrogen purging.
実施例5
(1)低屈折層製造用光硬化性コーティング組成物の製造
トリメチロールプロパントリアクリレート(TMPTA)100重量部に対して、中空状シリカナノ粒子(直径:約50〜60nm、密度:1.96g/cm3、JSC catalyst and chemicals社製品)268重量部、ソリッド状シリカナノ粒子(直径:約12nm、密度:2.65g/cm3)55重量部、第1含フッ素化合物(X−71−1203M、ShinEtsu社)144重量部、第2含フッ素化合物(RS−537、DIC社)21重量部、開始剤(Irgacure127、Ciba社)31重量部を、MIBK(methyl isobutyl ketone)溶媒に固形分濃度3重量%となるように希釈した。
Example 5
(1) Production of photocurable coating composition for production of low refractive layer Hollow silica nanoparticles (diameter: about 50-60 nm, density: 1.96 g / cm) with respect to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) 3 , JSC catalyst and chemicals product) 268 parts by weight, solid silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cm 3 ) 55 parts by weight, first fluorine-containing compound (X-71-1203M, ShinEtsu Corporation) ) 144 parts by weight, 21 parts by weight of a second fluorine-containing compound (RS-537, DIC), 31 parts by weight of an initiator (Irgacure 127, Ciba), and a solid concentration of 3% by weight in MIBK (methyl isobutyl ketone) solvent. Diluted to
(2)低屈折層および反射防止フィルムの製造
前記製造例のハードコートフィルム上に、前記得られた光硬化性コーティング組成物を#4mayer barで厚さが約110〜120nmとなるようにコーティングし、下記表1の温度および時間で乾燥および硬化した。前記硬化時には、窒素パージング下、前記乾燥したコーティング物に252mJ/cm2の紫外線を照射した。
(2) Production of Low Refractive Layer and Antireflection Film On the hard coat film of the production example, the obtained photocurable coating composition was coated with # 4mayer bar so that the thickness was about 110 to 120 nm. These were dried and cured at the temperatures and times shown in Table 1 below. During the curing, the dried coating was irradiated with 252 mJ / cm 2 of ultraviolet light under nitrogen purging.
実施例6
(1)ハードコート層(HD2)の製造
ペンタエリスリトールトリアクリレート30g、高分子量共重合体(BEAMSET371、Arakawa社、Epoxy Acrylate、分子量40,000)2.5g、メチルエチルケトン20g、およびレベリング剤(Tego wet270)0.5gを均一に混合した後に、屈折率が1.525の微粒子としてアクリル−スチレン共重合体(体積平均粒径:2μm、製造会社:Sekisui Plastic)2gを添加して、ハードコート組成物を製造した。
Example 6
(1) Production of hard coat layer (HD2) 30 g of pentaerythritol triacrylate, high molecular weight copolymer (BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000) 2.5 g, 20 g of methyl ethyl ketone, and a leveling agent (Tego wet 270) After uniformly mixing 0.5 g, 2 g of acrylic-styrene copolymer (volume average particle size: 2 μm, manufacturer: Sekisui Plastic) is added as fine particles having a refractive index of 1.525, and a hard coat composition is prepared. Manufactured.
こうして得られたハードコート組成物をトリアセチルセルロースフィルムに#10mayer barでコーティングし、90℃で1分間乾燥した。前記乾燥物に150mJ/cm2の紫外線を照射して、5μmの厚さを有するハードコート層を製造した。 The hard coat composition thus obtained was coated on a triacetyl cellulose film with # 10 mayer bar and dried at 90 ° C. for 1 minute. The dried product was irradiated with ultraviolet rays of 150 mJ / cm 2 to produce a hard coat layer having a thickness of 5 μm.
(2)低屈折層および反射防止フィルムの製造
ペンタエリスリトールトリアクリレート(PETA)100重量部に対して、中空状シリカナノ粒子(直径:約50〜60nm、密度:1.96g/cm3、JGC catalyst and chemicals社製品)135重量部、ソリッド状シリカナノ粒子(直径:約12nm、密度:2.65g/cm3)88重量部、第1含フッ素化合物(X−71−1203M、ShinEtsu社)38重量部、第2含フッ素化合物(RS−537、DI社)11重量部、開始剤(Irgacure127、Ciba社)7重量部を、メチルイソブチルケトン(MIBK):ジアセトンアルコール(DAA):イソプロピルアルコールを3:3:4の重量比で混合した溶媒に固形分濃度3重量%となるように希釈して、低屈折層製造用光硬化性コーティング組成物を製造した。
(2) Production of Low Refractive Layer and Antireflection Film Hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cm 3 , JGC catalyst and and with respect to 100 parts by weight of pentaerythritol triacrylate (PETA) chemicals product) 135 parts by weight, solid silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cm 3 ) 88 parts by weight, first fluorine-containing compound (X-71-1203M, ShinEtsu) 38 parts by weight, 11 parts by weight of second fluorine-containing compound (RS-537, DI), 7 parts by weight of initiator (Irgacure 127, Ciba), methyl isobutyl ketone (MIBK): diacetone alcohol (DAA): isopropyl alcohol 3: 3 : Solid content concentration of 3 weights in a solvent mixed at a weight ratio of 4 And diluted to a, to produce a low-refractive layer produced photocurable coating composition.
前記製造されたハードコート層(HD2)上に、前記得られた低屈折層製造用光硬化性コーティング組成物を#4mayer barで厚さが約110〜120nmとなるようにコーティングし、60℃の温度で1分間乾燥および硬化した。前記硬化時には、窒素パージング下、前記乾燥したコーティング物に252mJ/cm2の紫外線を照射した。 The obtained hard coat layer (HD2) is coated with the obtained photocurable coating composition for producing a low refractive layer so as to have a thickness of about 110 to 120 nm with # 4 mayer bar. Dried and cured at temperature for 1 minute. During the curing, the dried coating was irradiated with 252 mJ / cm 2 of ultraviolet light under nitrogen purging.
<比較例:反射防止フィルムの製造>
比較例1
前記低屈折層製造用光硬化性コーティング組成物を塗布し、常温(25℃)で乾燥した点を除いて、実施例1と同様の方法で反射防止フィルムを製造した。
<Comparative example: Production of antireflection film>
Comparative Example 1
An antireflection film was produced in the same manner as in Example 1, except that the photocurable coating composition for producing the low refractive layer was applied and dried at room temperature (25 ° C.).
比較例2
前記実施例1で用いたソリッド状シリカナノ粒子63重量部をペンタエリスリトールトリアクリレート(PETA)63重量部に代替した点を除いて、前記実施例1と同様の方法で低屈折層製造用光硬化性コーティング組成物を製造し、実施例1と同様の方法で反射防止フィルムを製造した。
Comparative Example 2
Except that 63 parts by weight of the solid silica nanoparticles used in Example 1 are replaced with 63 parts by weight of pentaerythritol triacrylate (PETA), photocurability for producing a low refractive layer is obtained in the same manner as in Example 1. A coating composition was produced, and an antireflection film was produced in the same manner as in Example 1.
比較例3
前記低屈折層製造用光硬化性コーティング組成物を塗布し、約140℃で乾燥した点を除いて、実施例5と同様の方法で反射防止フィルムを製造した。
Comparative Example 3
An antireflective film was produced in the same manner as in Example 5 except that the photocurable coating composition for producing the low refractive layer was applied and dried at about 140 ° C.
<実験例:反射防止フィルムの物性の測定>
前記実施例および比較例で得られた反射防止フィルムに対して、次の項目の実験を施した。
<Experimental example: measurement of physical properties of antireflection film>
The following items of experiments were performed on the antireflection films obtained in the examples and comparative examples.
1.反射防止フィルムの反射率の測定
実施例および比較例で得られた反射防止フィルムが可視光線領域(380〜780nm)で示す平均反射率を、Solidspec3700(SHIMADZU)装備を用いて測定した。
1. Measurement of reflectance of antireflection film The average reflectance exhibited by the antireflection films obtained in Examples and Comparative Examples in the visible light region (380 to 780 nm) was measured using a Solidspec 3700 (SHIMADZU) equipment.
2.防汚性の測定
実施例および比較例で得られた反射防止フィルムの表面に黒ネームペンで5cmの長さの直線を描き、無塵布を用いて擦った時の消される回数を確認して、防汚性を測定した。
2. Measurement of antifouling property Draw a straight line with a length of 5 cm with a black name pen on the surface of the antireflection film obtained in Examples and Comparative Examples, and confirm the number of times it is erased when rubbed with a dust-free cloth. The antifouling property was measured.
<測定基準>
O:消された時点が10回以下
△:消された時点が11回〜20回
X:消された時点が20回超過
<Measurement standard>
O: Time of disappearance is 10 times or less. Δ: Time of disappearance is 11 to 20 times. X: Time of disappearance exceeds 20 times.
3.耐スクラッチ性の測定
前記スチールウールに荷重をかけて27rpmの速度で10回往復し、実施例および比較例で得られた反射防止フィルムの表面を擦った。肉眼で観察される1cm以下のスクラッチ1個以下が観察される最大荷重を測定した。
3. Measurement of scratch resistance The steel wool was loaded and reciprocated 10 times at a speed of 27 rpm, and the surfaces of the antireflection films obtained in Examples and Comparative Examples were rubbed. The maximum load at which one scratch or less of 1 cm or less observed with the naked eye was observed was measured.
4.相分離の有無の確認
図1〜7の反射防止フィルムの断面において、ハードコート層から30nm以内に使用したソリッド状無機ナノ粒子(ソリッド状ナノシリカ粒子)全体中の70体積%が存在する場合、相分離が起こったと決定した。
4). Confirmation of presence or absence of phase separation In the cross section of the antireflection film of FIGS. 1 to 7, when 70% by volume of the whole solid inorganic nanoparticles (solid nanosilica particles) used within 30 nm from the hard coat layer is present, It was determined that separation occurred.
5.屈折率の測定
前記実施例で得られた低屈折率層のうち、相分離された領域に対して380nm〜1,000nmの波長で測定された楕円偏光とCauchyモデルを用いて、550nmにおける屈折率を計算した。
5. Refractive Index Measurement Among the low refractive index layers obtained in the above examples, the refractive index at 550 nm using elliptically polarized light measured at a wavelength of 380 nm to 1,000 nm with respect to the phase-separated region and the Cauchy model. Was calculated.
具体的には、前記実施例それぞれで得られた低屈折率層に対して、J.A.Woollam Co.M−2000の装置を用いて、70°の入射角を適用し、380nm〜1000nmの波長範囲で線偏光を測定した。前記測定された線偏光測定データ(Ellipsometry data(Ψ、Δ))を、Complete EASE softwareを用いて、前記低屈折率層の第1、第2層(Layer1、Layer2)に対して、下記一般式1のコーシーモデル(Cauchy model)でMSEが3以下となるように最適化(fitting)した。 Specifically, for the low refractive index layer obtained in each of the above examples, J.A. A. Woollam Co. Using an M-2000 apparatus, an incident angle of 70 ° was applied, and linearly polarized light was measured in a wavelength range of 380 nm to 1000 nm. The measured linear polarimetry data (Ellipsometry data (Ψ, Δ)) is expressed by the following general formula for the first and second layers (Layer 1 and Layer 2) of the low refractive index layer using Complete EASE software. With 1 Cauchy model, the MSE was optimized to be 3 or less.
前記一般式1において、n(λ)は、λ波長における屈折率(refractive index)であり、λは、300nm〜1800nmの範囲であり、A、BおよびCは、コーシーパラメータである。 In the general formula 1, n (λ) is a refractive index at λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B, and C are Cauchy parameters.
6.Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)
X線反射率は1cm×1cm(横×縦)の大きさの反射防止フィルムに対して、1.5418Åの波長のCu−Kα線を照射して測定した。具体的には、使用装置はPANalytical X’Pert Pro MRD XRDを用い、45kVの電圧および40mAの電流を適用した。使用したopticsは次の通りである。
6). Fourier transform analysis of X-ray reflectivity measurement results using Cu-Kα rays (Fourier transform analysis)
X-ray reflectivity was measured by irradiating an antireflection film having a size of 1 cm × 1 cm (width × length) with Cu—Kα rays having a wavelength of 1.5418 mm. Specifically, the apparatus used was a PANalytical X'Pert Pro MRD XRD, and a voltage of 45 kV and a current of 40 mA were applied. The optics used are as follows.
−Incident beam optic:Primary mirror、Auto Attenuator、1/16°FDS
−Diffracted beam optic:Parallel plate collimator(PPC) with silt(0.27)
−Soller slit(0.04rad)、Xe counter
-Incident beam optic: Primary mirror, Auto Attenuator, 1/16 ° FDS.
-Diffracted beam optic: Parallel plate collimator (PPC) with silt (0.27)
-Seller slit (0.04 rad), Xe counter
そして、2theta(2θ)値が0となるようにサンプルステージを調整した後、サンプルのhalf−cutを確認し、この後、入射角と反射角がspecular条件を満足する状態に設定し、Z⇒Omega⇒Z alignをしてX線反射率を測定できるように用意して、2θが0.2°から3.2°まで0.004°の間隔で測定する。これによって、X線反射率パターンを測定した。 Then, after adjusting the sample stage so that the 2theta (2θ) value becomes 0, the half-cut of the sample is confirmed, and thereafter, the incident angle and the reflection angle are set to satisfy the special condition, and Z⇒ Prepare so that X-ray reflectivity can be measured by performing Omega => Z alignment, and 2 [theta] is measured at intervals of 0.004 [deg.] From 0.2 [deg.] To 3.2 [deg.]. Thereby, the X-ray reflectivity pattern was measured.
前記Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析は、PANalytical社のX’pert Reflectivityプログラムを用いて行い、フーリエ変換時、input値として、star tangleには0.1°を入力し、end angleには1.2°を入力し、critical angleには0.163°を入力した。 The Fourier transform analysis of the measurement result of the X-ray reflectivity by the Cu-Kα ray is performed using the X'pert Reflectivity program of PANalytical, and 0.1 ° is input as the input value at the time of the Fourier transform. In the end angle, 1.2 ° was input, and in the critical angle, 0.163 ° was input.
[P1]および[P2]はそれぞれ、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、Y軸のフーリエ変換強度の極点が現れる厚さ(thickness)である。 [P1] and [P2] are thicknesses where the extreme points of the Fourier transform intensity on the Y axis appear in the Fourier transform analysis result graph for the X-ray reflectivity measurement result by Cu-Kα ray, respectively. It is.
実施例1〜6の反射防止フィルムは、図10〜15から確認されるように、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、35nm〜55nmの厚さ(thickness)で1つのフーリエ変換強度の極値を示し、85nm〜105nmの厚さ(thickness)で1つのフーリエ変換強度の極値を示すが、前記表2に示されているように、実施例の反射防止フィルムは、可視光線領域で0.70%以下の低い反射率を示しかつ、高い耐スクラッチ性および防汚性を同時に実現できる点が確認された。 As is confirmed from FIGS. 10 to 15, the antireflection films of Examples 1 to 6 are 35 nm to 55 nm in a Fourier transform analysis result graph with respect to the measurement result of the X-ray reflectance by Cu—Kα ray. The thickness (thickness) of one Fourier transform intensity indicates an extreme value, and the thickness (thickness) of 85 nm to 105 nm indicates one Fourier transform intensity extreme value, as shown in Table 2 above. In addition, it was confirmed that the antireflection films of the examples exhibited a low reflectance of 0.70% or less in the visible light region, and could simultaneously realize high scratch resistance and antifouling properties.
また、図1〜6に示されているように、実施例1〜6の反射防止フィルムの低屈折層では、中空状無機ナノ粒子およびソリッド状無機ナノ粒子が相分離されており、前記ソリッド状無機ナノ粒子が前記反射防止フィルムのハードコート層および前記低屈折層の間の界面側に大部分存在して集中しており、前記中空状無機ナノ粒子はハードコート層から遠い側に大部分存在して集中している点が確認される。 Also, as shown in FIGS. 1 to 6, in the low refractive layers of the antireflection films of Examples 1 to 6, hollow inorganic nanoparticles and solid inorganic nanoparticles are phase-separated, and the solid state Inorganic nanoparticles are mostly present and concentrated on the interface side between the hard coat layer and the low refractive layer of the antireflection film, and the hollow inorganic nanoparticles are mostly present on the side far from the hard coat layer. And the point that is concentrated is confirmed.
さらに、前記表3に示されているように、実施例の低屈折層において、中空状無機ナノ粒子およびソリッド状無機ナノ粒子が相分離されて区分される第1領域および第2領域は、異なる範囲の屈折率を示し、具体的には、ソリッド状無機ナノ粒子が主に分布する第1領域は、1.420以上の屈折率を示し、中空状無機ナノ粒子が主に分布する第2領域は、1.400以下の屈折率を示す点が確認された。 Furthermore, as shown in Table 3, the first region and the second region in which the hollow inorganic nanoparticles and the solid inorganic nanoparticles are separated and separated in the low refractive layer of the example are different. Specifically, the first region in which the solid inorganic nanoparticles are mainly distributed has a refractive index of 1.420 or more, and the second region in which the hollow inorganic nanoparticles are mainly distributed. Was confirmed to have a refractive index of 1.400 or less.
このように、これに対し、図7〜9に示されているように、比較例1〜3の反射防止フィルムの低屈折層では、中空状無機ナノ粒子およびソリッド状無機ナノ粒子が相分離されずに混在している点が確認される。 Thus, as shown in FIGS. 7 to 9, in the low-refractive layer of the antireflection films of Comparative Examples 1 to 3, the hollow inorganic nanoparticles and the solid inorganic nanoparticles are phase-separated. A mixed point is confirmed.
また、前記表2および図16〜18に示されているように、比較例1〜3の反射防止フィルムの低屈折層は、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、35nm〜55nmの厚さ(thickness)および85nm〜105nmの2つの厚さ(thickness)範囲でいずれも極点を示しておらず、また、相対的に高い反射率を示しかつ、低い耐スクラッチ性および防汚性を有する点が確認された。 Moreover, as shown in the said Table 2 and FIGS. 16-18, the low-refractive layer of the antireflection film of Comparative Examples 1-3 is a Fourier-transform analysis with respect to the measurement result of the X-ray reflectivity by a Cu-K (alpha) ray ( In the Fourier transform analysis graph, no poles are shown in the thickness range of 35 nm to 55 nm and two thickness ranges of 85 nm to 105 nm, and relatively high reflectivity is shown. And the point which has low scratch resistance and antifouling property was confirmed.
本明細書では、Cu−Kα線によるX線反射率の測定結果に対するフーリエ変換解析(Fourier transform analysis)結果グラフにおいて、表面から35nm〜55nmの厚さ(thickness)で1つの極値を示し、表面から85nm〜105nmの厚さ(thickness)で1つの極値を示す、反射防止フィルムが提供される。
また、本明細書では、ハードコーティング層;及びバインダー樹脂と前記バインダー樹脂に分散した中空状無機ナノ粒子及びソリッド状無機ナノ粒子を含む低屈折層;を含み、前記低屈折層は、1.420以上の屈折率を示す第1領域と1.400以下の屈折率を示す第2領域とを含む反射防止フィルムが提供される。
前記第1領域は、前記ソリッド状無機ナノ粒子全体中の70体積%以上を含み、前記第2領域は、前記中空状無機ナノ粒子全体中の70体積%以上を含み得る。
前記第1領域が、前記第2領域に比べて、前記ハードコーティング層及び前記低屈折層の間の界面により近く位置し得る。
前記低屈折層に含まれている第2領域に対して楕円偏光法(ellipsometry)で測定した偏極の楕円率を下記一般式1のコーシーモデル(Cauchy model)で最適化(fitting)した時、下記Aは1.0〜1.50、Bは0〜0.007、Cは0〜1×10 −3 の条件を満足することができる。
前記低屈折層に含まれている第1領域に対して楕円偏光法(ellipsometry)で測定した偏極の楕円率を下記一般式1のコーシーモデル(Cauchy model)で最適化(fitting)した時、下記Aは1.0〜1.65、Bは0.0010〜0.0350、Cは0〜1×10 −3 の条件を満足することができる。
前記ソリッド状無機ナノ粒子が前記中空状無機ナノ粒子に比べて0.50g/cm 3 以上高い密度を有することができる。
前記低屈折層に含まれるバインダー樹脂は、光重合性化合物の(共)重合体及び光反応性官能基を含む含フッ素化合物の間の架橋(共)重合体を含むことができる。
前記低屈折層は、前記光重合性化合物の(共)重合体100重量部対比、前記中空状無機ナノ粒子10〜400重量部及び前記ソリッド状無機ナノ粒子10〜400重量部を含むことができる。
前記光反応性官能基を含む含フッ素化合物は、それぞれ2,000〜200,000の重量平均分子量を有することができる。
前記バインダー樹脂は、前記光重合性化合物の(共)重合体100重量部に対して、前記光反応性官能基を含む含フッ素化合物を20〜300重量部で含むことができる。
前記ハードコーティング層は、光硬化性樹脂を含むバインダー樹脂及び前記バインダー樹脂に分散した有機または無機微粒子;を含むことができる。
前記有機微粒子は、1〜10μmの粒径を有し、前記無機微粒子は、1nm〜500nmの粒径を有することができる。
In this specification, in the Fourier transform analysis (Fourier transform analysis) result graph with respect to the measurement result of the X-ray reflectivity by Cu-Kα ray, one extreme value is shown with a thickness (thickness) of 35 nm to 55 nm from the surface. An antireflective film is provided that exhibits one extreme at a thickness of from 85 nm to 105 nm.
Further, the present specification includes a hard coating layer; and a low refractive layer containing a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin; There is provided an antireflection film including a first region exhibiting the above refractive index and a second region exhibiting a refractive index of 1.400 or less.
The first region may include 70% by volume or more in the entire solid inorganic nanoparticles, and the second region may include 70% by volume or more in the entire hollow inorganic nanoparticles.
The first region may be located closer to the interface between the hard coating layer and the low refractive layer than the second region.
When the ellipticity of polarization measured by elliptic polarization with respect to the second region included in the low refractive layer is optimized with a Cauchy model of the following general formula 1, The following A can satisfy the conditions of 1.0 to 1.50, B can satisfy 0 to 0.007, and C can satisfy 0 to 1 × 10 −3 .
When the ellipticity of polarization measured by elliptic polarization with respect to the first region included in the low refractive layer is optimized with a Cauchy model of the following general formula 1, The following A can satisfy the condition of 1.0 to 1.65, B can satisfy the condition of 0.0010 to 0.0350, and C can satisfy the condition of 0 to 1 × 10 −3 .
The solid inorganic nanoparticles may have a density higher by 0.50 g / cm 3 or more than the hollow inorganic nanoparticles .
The binder resin contained in the low refractive layer can include a crosslinked (co) polymer between a (co) polymer of a photopolymerizable compound and a fluorine-containing compound containing a photoreactive functional group.
The low refractive layer may include 100 parts by weight of the (co) polymer of the photopolymerizable compound, 10 to 400 parts by weight of the hollow inorganic nanoparticles, and 10 to 400 parts by weight of the solid inorganic nanoparticles. .
Each of the fluorine-containing compounds containing the photoreactive functional group may have a weight average molecular weight of 2,000 to 200,000.
The binder resin may contain 20 to 300 parts by weight of the fluorine-containing compound containing the photoreactive functional group with respect to 100 parts by weight of the (co) polymer of the photopolymerizable compound.
The hard coating layer may include a binder resin including a photocurable resin and organic or inorganic fine particles dispersed in the binder resin.
The organic fine particles may have a particle size of 1 to 10 μm, and the inorganic fine particles may have a particle size of 1 nm to 500 nm.
Claims (20)
表面から35nm〜55nmの厚さ(thickness)で1つの極値を示し、表面から85nm〜105nmの厚さ(thickness)で1つの極値を示す、反射防止フィルム。 In the Fourier transform analysis (Fourier transform analysis) result graph for the measurement result of the X-ray reflectivity by Cu-Kα ray,
The antireflection film which shows one extreme value by the thickness (thickness) of 35 nm-55 nm from the surface, and shows one extreme value by the thickness (thickness) of 85 nm-105 nm from the surface.
前記表面から35nm〜55nmの厚さおよび85nm〜105nmそれぞれは、前記低屈折層の表面からの厚さである、請求項1に記載の反射防止フィルム。 The antireflection film includes a hard coat layer; and a low refractive layer formed on the hard coat layer;
2. The antireflection film according to claim 1, wherein each of a thickness of 35 nm to 55 nm and a thickness of 85 nm to 105 nm from the surface is a thickness from the surface of the low refractive layer.
前記第1層が、第2層に比べて、前記ハードコート層および前記低屈折層の間の界面により近く位置する、請求項6に記載の反射防止フィルム。 The low-refractive layer includes a first layer containing 70% by volume or more of the whole solid inorganic nanoparticles and a second layer containing 70% by volume or more of the whole hollow inorganic nanoparticles. Including
The antireflection film according to claim 6, wherein the first layer is located closer to an interface between the hard coat layer and the low refractive layer than the second layer.
前記無機微粒子は、1nm〜500nmの粒径を有する、請求項19に記載の反射防止フィルム。 The organic fine particles have a particle size of 1 to 10 μm,
The antireflection film according to claim 19, wherein the inorganic fine particles have a particle diameter of 1 nm to 500 nm.
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